JP5071578B2 - Preparation method of coal for coke production - Google Patents

Preparation method of coal for coke production Download PDF

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JP5071578B2
JP5071578B2 JP2011187113A JP2011187113A JP5071578B2 JP 5071578 B2 JP5071578 B2 JP 5071578B2 JP 2011187113 A JP2011187113 A JP 2011187113A JP 2011187113 A JP2011187113 A JP 2011187113A JP 5071578 B2 JP5071578 B2 JP 5071578B2
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JP2012072391A (en
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泉 下山
勇介 土肥
喜代志 深田
哲也 山本
広行 角
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/26—After-treatment of the shaped fuels, e.g. briquettes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization

Description

この発明は石炭乾留時の軟化溶融特性を精度良く評価する試験方法を用いてコークス製造用石炭を評価し、その結果に基づいて、コークス強度を向上させることのできる、コークス製造用石炭を調製する方法に関する。     This invention evaluates the coal for coke production using a test method for accurately evaluating the softening and melting characteristics during coal dry distillation, and based on the result, prepares the coal for coke production that can improve the coke strength. Regarding the method.

製銑法として最も一般的に行われている高炉法において使用されるコークスは、鉄鉱石の還元材、熱源、スペーサーなどの数々の役割を担っている。高炉を安定的に効率良く操業するためには、高炉内の通気性を維持することが重要であることから、強度の高いコークスの製造が求められている。コークスは、粉砕し、粒度を調整した種々のコークス製造用石炭を配合した配合炭を、コークス炉内にて乾留することで製造される。コークス製造用石炭は、乾留中約３００℃〜５５０℃の温度域で軟化溶融し、また同時に揮発分の発生に伴い発泡、膨張することで、各々の粒子が互いに接着しあい、塊状のセミコークスとなる。セミコークスは、その後１０００℃付近まで昇温する過程で収縮することで焼きしまり、堅牢なコークスとなる。従って、石炭の軟化溶融時の接着特性が、乾留後のコークス強度や粒径等の性状に大きな影響を及ぼす。   Coke used in the blast furnace method, which is most commonly used as a steelmaking method, plays a number of roles, such as iron ore reductant, heat source, and spacer. In order to operate the blast furnace stably and efficiently, it is important to maintain the air permeability in the blast furnace, and therefore production of coke having high strength is required. Coke is produced by dry-distilling blended coal in which various types of coal for coke production, which are pulverized and adjusted in particle size, are blended in a coke oven. Coal-producing coal softens and melts in the temperature range of about 300 ° C to 550 ° C during dry distillation, and at the same time foams and expands with the generation of volatile matter. Become. Semi-coke is burned by shrinkage in the process of raising the temperature to around 1000 ° C., and becomes robust coke. Therefore, the adhesion characteristics during softening and melting of coal greatly affect properties such as coke strength and particle size after dry distillation.

上述のとおり、石炭の軟化溶融特性は、乾留後のコークス性状やコークスケーキ構造を大きく左右するため、極めて重要であり、古くからその測定方法の検討が盛んになされてきた。特に、コークスの重要な品質であるコークス強度は、その原料である石炭性状、とりわけ石炭化度と軟化溶融特性に大きく影響される。軟化溶融特性とは、石炭を加熱したときに軟化溶融する性質であり、通常、軟化溶融物の流動性、粘度、接着性、膨張性などにより測定、評価される。   As described above, the softening and melting characteristics of coal are extremely important because they greatly affect the coke properties and coke cake structure after carbonization, and the investigation of the measurement method has been actively conducted for a long time. In particular, coke strength, which is an important quality of coke, is greatly affected by the properties of coal as the raw material, particularly the degree of coalification and softening and melting characteristics. The softening and melting property is a property of softening and melting when coal is heated, and is usually measured and evaluated by the fluidity, viscosity, adhesiveness, expandability, etc. of the softened melt.

石炭の軟化溶融特性のうち、軟化溶融時の流動性を測定する一般的な方法としては、ＪＩＳ Ｍ ８８０１に規定されるギーセラープラストメータ法による石炭流動性試験方法が挙げられる。ギーセラープラストメータ法は、４２５μｍ以下に粉砕した石炭を所定のるつぼに入れ、規定の昇温速度で加熱し、規定のトルクをかけた撹拌棒の回転速度を目盛板で読み取り、ddpm(dial division per minute)で表示する方法である。   Among the softening and melting characteristics of coal, a general method for measuring the fluidity at the time of softening and melting includes a coal fluidity test method by the Gieseler plastometer method defined in JIS M8801. In the Gieseler plastometer method, coal pulverized to 425 μm or less is put in a predetermined crucible, heated at a specified temperature increase rate, and the rotation speed of a stirring rod to which a specified torque is applied is read with a scale plate, and ddpm (dial division per minute).

ギーセラープラストメータ法がトルク一定での撹拌棒の回転速度を測定しているのに対し、定回転方式でトルクを測定する方法も考案されている。例えば、特許文献１では、回転子を一定の回転速度で回転させながらトルクを測定する方法が記載されている。   In contrast to the Gisela plastometer method, which measures the rotational speed of the stirring rod with a constant torque, a method for measuring the torque by the constant rotation method has also been devised. For example, Patent Document 1 describes a method of measuring torque while rotating a rotor at a constant rotational speed.

また、軟化溶融特性として物理的に意味のある粘性を測定することを目的にした、動的粘弾性測定装置による粘度の測定方法がある（例えば、特許文献２参照。）。動的粘弾性測定とは、粘弾性体に周期的に力を加えたときに見られる粘弾性挙動の測定である。特許文献２に記載の方法では、測定で得られるパラメータ中の複素粘性率により軟化溶融石炭の粘性を評価しており、任意のせん断速度における軟化溶融石炭の粘度を測定可能な点が特徴である。   In addition, there is a viscosity measurement method using a dynamic viscoelasticity measuring device for the purpose of measuring a physically meaningful viscosity as a softening and melting characteristic (see, for example, Patent Document 2). Dynamic viscoelasticity measurement is the measurement of viscoelastic behavior seen when a force is applied periodically to a viscoelastic body. The method described in Patent Document 2 is characterized in that the viscosity of the softened molten coal is evaluated by the complex viscosity in the parameters obtained by the measurement, and the viscosity of the softened molten coal at an arbitrary shear rate can be measured. .

さらに、石炭の軟化溶融特性として、活性炭、またはガラスビーズを用い、それらへの石炭軟化溶融物接着性を測定した例が報告されている。少量の石炭試料を活性炭、ガラスビーズで上下方向から挟んだ状態で加熱し、軟化溶融後に冷却を行い、石炭と活性炭、ガラスビーズとの接着性を外観から観察する方法である。   Furthermore, as an example of the softening and melting characteristics of coal, an example in which activated carbon or glass beads was used and the coal softening melt adhesion to them was measured was reported. In this method, a small amount of coal sample is heated while being sandwiched between activated carbon and glass beads from above and below, cooled after softening and melting, and the adhesion between coal, activated carbon and glass beads is observed from the appearance.

石炭の軟化溶融時の膨張性を測定する一般的な方法としては、ＪＩＳ Ｍ ８８０１に規定されているジラトメーター法が挙げられる。ジラトメーター法は、２５０μｍ以下に粉砕した石炭を規定の方法で成型し、所定のるつぼに入れ、規定の昇温速度で加熱し、石炭の上部に配置した検出棒で、石炭の変位の経時変化を測定する方法である。   A general method for measuring the expansibility of coal during soft melting is the dilatometer method defined in JIS M8801. In the dilatometer method, coal pulverized to 250 μm or less is molded by a specified method, placed in a predetermined crucible, heated at a specified rate of temperature rise, and a detection rod placed on the top of the coal is used to measure changes in coal displacement over time. It is a method of measuring.

さらに、コークス炉内での石炭軟化溶融挙動を模擬するため、石炭軟化溶融時に発生するガスの透過挙動を改善した石炭膨張性試験方法も知られている（例えば、特許文献３参照）。これは、石炭層とピストンの間、もしくは石炭層とピストンの間と石炭層の下部に透過性材料を配置し、石炭から発生する揮発分と液状物質の透過経路を増やすことで、測定環境を、よりコークス炉内の膨張挙動に近づけた方法である。同様に、石炭層の上に貫通経路を有する材料を配置し、荷重を負荷しながら石炭をマイクロ波加熱して石炭の膨張性を測定する方法も知られている（特許文献４参照。）。   Furthermore, in order to simulate the behavior of coal softening and melting in a coke oven, a coal expansibility test method that improves the permeation behavior of gas generated during softening and melting of coal is also known (see, for example, Patent Document 3). This is because the permeable material is placed between the coal bed and the piston, or between the coal bed and the piston and below the coal bed, and the passage of volatiles and liquid substances generated from the coal is increased, thereby reducing the measurement environment. This is a method closer to the expansion behavior in the coke oven. Similarly, a method is also known in which a material having a through-passage is disposed on a coal bed, and the coal is microwave-heated while applying a load to measure the expansibility of the coal (see Patent Document 4).

特開平６−３４７３９２号公報JP-A-6-347392 特開２０００−３０４６７４号公報JP 2000-304673 A 特許第２８５５７２８号公報Japanese Patent No. 2855728 特開２００９−２０４６０９号公報JP 2009-204609 A

諸富ら著：「燃料協会誌」、Ｖｏｌ．５３、１９７４年、ｐ．７７９−７９０Morotomi et al .: “Journal of Fuel Association”, Vol. 53, 1974, p. 779-790 宮津ら著：「日本鋼管技報」、ｖｏｌ．６７、１９７５年、ｐ．１２５−１３７Miyazu et al .: “Nippon Steel Pipe Technical Report”, vol. 67, 1975, p. 125-137

冶金用コークスの製造においては、複数の銘柄の石炭を所定の割合で配合した配合炭を使用するのが一般的であるが、軟化溶融特性を正しく評価できないと、要求されているコークス強度を満足することができないという問題がある。高炉等の竪型炉で所定の強度を満足していない低強度のコークスを使用した場合、竪型炉内での粉の発生量を増加させて圧力損失の増大を招き、竪型炉の操業を不安定化させるとともにガスの流れが局所的に集中する、いわゆる吹き抜けといったトラブルを招く可能性がある。   In the manufacture of metallurgical coke, it is common to use blended coal that is a mixture of several brands of coal at a specified ratio. However, if the softening and melting characteristics cannot be evaluated correctly, the required coke strength is satisfied. There is a problem that you can not. When low-strength coke that does not satisfy the specified strength is used in a vertical furnace such as a blast furnace, the amount of powder generated in the vertical furnace is increased, resulting in an increase in pressure loss and the operation of the vertical furnace. May cause troubles such as so-called blow-through, in which the gas flow is locally concentrated.

従来の軟化溶融特性指標は、強度を正確に予測することが出来ない場合も少なくない。そのため、経験的に、軟化溶融特性の評価の不正確さに由来するコークス強度のバラツキを考慮して、目標とするコークス強度を予め高めに設定することでコークス強度を一定値以上に管理することが行われている。しかし、この方法では、一般的に知られている軟化溶融特性に優れた、比較的高価な石炭を使用して配合炭の平均的な品位を高めに設定することが必要となるため、コストの増大を招く。   Conventional softening and melting characteristics indicators often cannot accurately predict strength. Therefore, empirically, the coke strength is controlled to a certain value or higher by setting the target coke strength higher in advance in consideration of the variation in coke strength resulting from inaccuracy of the evaluation of softening and melting characteristics. Has been done. However, in this method, it is necessary to use a relatively expensive coal having excellent softening and melting characteristics, which is generally known, and to set the average quality of the blended coal to be higher, so that the cost is reduced. Incurs an increase.

コークス炉内において、軟化溶融時の石炭は隣接する層に拘束された状態で軟化溶融している。石炭の熱伝導率は小さいため、コークス炉内において石炭は一様に加熱されず、加熱面である炉壁側からコークス層、軟化溶融層、石炭層と状態が異なっている。コークス炉自体は乾留時多少膨張するがほとんど変形しないため、軟化溶融した石炭は隣接するコークス層、石炭層に拘束されている。   In the coke oven, the coal at the time of softening and melting is softened and melted while being constrained by adjacent layers. Since the thermal conductivity of coal is small, the coal is not uniformly heated in the coke oven, and the state differs from the coke layer, the softened molten layer, and the coal layer from the furnace wall side that is the heating surface. Since the coke oven itself expands somewhat during dry distillation but hardly deforms, the softened and melted coal is constrained by the adjacent coke layer and coal layer.

また、軟化溶融した石炭の周囲には、石炭層の石炭粒子間空隙、軟化溶融石炭の粒子間空隙、熱分解ガスの揮発により発生した粗大気孔、隣接するコークス層に生じる亀裂など、多数の欠陥構造が存在する。特に、コークス層に生じる亀裂は、その幅が数百ミクロンから数ミリ程度と考えられ、数十〜数百ミクロン程度の大きさである石炭粒子間空隙や気孔に比較して大きい。従って、このようなコークス層に生じる粗大欠陥へは、石炭から発生する副生物である熱分解ガスや液状物質だけではなく、軟化溶融した石炭自体の浸透も起こると考えられる。また、その浸透時に軟化溶融した石炭に作用するせん断速度は、銘柄毎に異なることが予想される。   In addition, there are many defects around the softened and melted coal, such as voids between coal particles in the coal bed, interparticle voids in the softened molten coal, rough air holes generated by volatilization of the pyrolysis gas, and cracks in the adjacent coke layer. Structure exists. In particular, the crack generated in the coke layer is considered to have a width of several hundred microns to several millimeters, and is larger than the voids and pores between coal particles having a size of about several tens to several hundreds of microns. Therefore, it is considered that coarse defects generated in such a coke layer are not only caused by pyrolysis gas and liquid substances, which are by-products generated from coal, but also permeate softened and melted coal itself. Further, it is expected that the shear rate acting on the softened and melted coal at the time of infiltration varies from brand to brand.

発明者らは、コークスの強度をより精度よく制御するためには、上記のような石炭がコークス炉内で置かれる環境を模擬した条件で測定される石炭軟化溶融特性を指標として用いる必要があると考えた。なかでも、軟化溶融した石炭が拘束された条件で、かつ周囲の欠陥構造への溶融物の移動、浸透を模擬した条件で測定することが重要であると考えた。しかし、従来の測定方法には以下のような問題があった。   In order to control the strength of coke more accurately, the inventors need to use the coal softening and melting characteristics measured under conditions simulating the environment in which the coal is placed in the coke oven as an index. I thought. In particular, it was important to measure under conditions where softened and melted coal was constrained, and under conditions simulating the movement and penetration of the melt into the surrounding defect structure. However, the conventional measuring method has the following problems.

ギーセラープラストメータ法は、石炭を容器に充填した状態での測定のため、拘束、浸透条件を全く考慮していない点で問題である。また、この方法は、高い流動性を示す石炭の測定には適さない。その理由は、高い流動性を示す石炭を測定する場合、容器内側壁部が空洞となる現象（Ｗｅｉｓｓｅｎｂｅｒｇ効果）が起こり、撹拌棒が空転し、流動性を正しく評価できない場合があるためである（例えば、非特許文献１参照。）。   The Giselaer plastometer method is problematic in that it does not take into account any restraint or infiltration conditions for measurement in a state where coal is filled in a container. Moreover, this method is not suitable for the measurement of coal showing high fluidity. The reason is that, when measuring coal showing high fluidity, a phenomenon that the inner wall of the container becomes hollow (Weissenberg effect) occurs, the stirrer may idle, and the fluidity may not be evaluated correctly ( For example, refer nonpatent literature 1.).

定回転方式でトルクを測定する方法についても同様に、拘束条件、浸透条件を考慮していない点で不備がある。また、せん断速度一定下での測定のため、上記で述べたように石炭の軟化溶融特性を正しく比較評価することができない。   Similarly, the method of measuring the torque by the constant rotation method is deficient in that the constraint condition and the penetration condition are not taken into consideration. In addition, because of the measurement under a constant shear rate, it is impossible to correctly compare and evaluate the softening and melting characteristics of coal as described above.

動的粘弾性測定装置は、軟化溶融特性として粘性を対象とし、任意のせん断速度下で粘度が測定可能な装置である。よって、測定時のせん断速度を、コークス炉内での石炭に作用する値に設定すれば、コークス炉内での軟化溶融石炭の粘度を測定可能である。しかし、各銘柄のコークス炉内でのせん断速度を予め測定、または推定することは通常は困難である。   The dynamic viscoelasticity measuring apparatus is an apparatus that targets viscosity as a softening and melting characteristic and can measure the viscosity under an arbitrary shear rate. Therefore, if the shear rate at the time of measurement is set to a value that acts on the coal in the coke oven, the viscosity of the softened molten coal in the coke oven can be measured. However, it is usually difficult to measure or estimate the shear rate in each coke oven in advance.

石炭の軟化溶融特性として、活性炭、またはガラスビーズを用い、それらへの接着性を測定する方法は、石炭層の存在について浸透条件を再現しようとしているものの、コークス層と粗大欠陥を模擬していない点で問題がある。また、拘束下での測定でない点でも不十分である。   The method of measuring the adhesion to coal using activated carbon or glass beads as the softening and melting characteristics of coal tries to reproduce the infiltration conditions for the presence of coal layer, but does not simulate the coke layer and coarse defects There is a problem in terms. Moreover, the point which is not a measurement under restraint is also insufficient.

特許文献３に記載されている透過性材料を用いた石炭膨張性試験方法においては、石炭から発生するガス、液状物質の移動を考慮しているが、軟化溶融した石炭自体の移動を考慮していない点で問題である。これは特許文献３で用いる透過性材料の透過度が、軟化溶融石炭が移動するほど十分に大きくないためである。本発明者らが実際に特許文献３に記載の試験を行ったところ、軟化溶融石炭の透過性材料への浸透は起こらなかった。したがって、軟化溶融石炭の透過性材料への浸透を起こさせるためには、新たな条件を考慮する必要がある。   In the coal expansibility test method using the permeable material described in Patent Document 3, the movement of gas and liquid substance generated from coal is considered, but the movement of softened and melted coal itself is considered. There is no problem in that. This is because the permeability of the permeable material used in Patent Document 3 is not large enough to move the softened molten coal. When the present inventors actually performed the test described in Patent Document 3, penetration of the softened molten coal into the permeable material did not occur. Therefore, it is necessary to consider new conditions in order to cause the soft molten coal to penetrate into the permeable material.

特許文献４にも同様に石炭層の上に貫通経路を有する材料を配置して石炭から発生するガス、液状物質の移動を考慮した石炭の膨張性測定方法が開示されているが、加熱方法に制約があるという問題点の他、コークス炉内における浸透現象を評価するための条件が明確になっていないという問題がある。さらに特許文献４では、石炭溶融物の浸透現象と軟化溶融挙動の関係が明確になっておらず、石炭溶融物の浸透現象と生成するコークスの品質との関係についての示唆も無く、良好な品質のコークスの製造について記載されているものではない。   Similarly, Patent Document 4 discloses a method for measuring the expansibility of coal in consideration of the movement of gas and liquid substances generated from coal by arranging a material having a through path on the coal bed. In addition to the problem of restrictions, there is a problem that the conditions for evaluating the infiltration phenomenon in the coke oven are not clear. Furthermore, in Patent Document 4, the relationship between the infiltration phenomenon of the coal melt and the softening and melting behavior is not clear, and there is no suggestion about the relationship between the infiltration phenomenon of the coal melt and the quality of the coke to be produced. It does not describe the production of coke.

このように、従来技術ではコークス炉内において軟化溶融した石炭及び粘結材の周辺の環境を十分に模擬した状態で、石炭及び粘結材の流動性、粘性、接着性、浸透性、浸透時膨張率、浸透時圧力などの軟化溶融特性を測定することができない。   As described above, in the prior art, the fluidity, viscosity, adhesiveness, permeability, and penetration of coal and binder are fully simulated in the environment around coal and binder that has been softened and melted in a coke oven. Softening and melting properties such as expansion rate and pressure during penetration cannot be measured.

したがって本発明の目的は、このような従来技術の課題を解決し、コークス炉内において軟化溶融した石炭の周辺の環境を十分に模擬した状態での石炭の軟化溶融特性を測定することで、石炭のより正確な軟化溶融特性評価方法を提供し、その方法を用いて高強度コークスを製造するのに好適な石炭銘柄の品質を明らかにし、そのような品質を持った銘柄の石炭を調製する方法を提供することである。   Accordingly, an object of the present invention is to solve such problems of the prior art and measure the softening and melting characteristics of coal in a state that sufficiently simulates the environment around the softened and melted coal in a coke oven. To provide a more accurate softening and melting property evaluation method, to clarify the quality of a coal brand suitable for producing high-strength coke by using the method, and to prepare a brand of coal having such quality Is to provide.

このような課題を解決するための本発明の特徴は以下の通りである。
［１］コークス製造原料として単独で、または他の石炭と配合して用いる個別銘柄の石炭を調製する際に、前記銘柄の石炭の浸透距離を所定の値以下に調整することを特徴とするコークス製造用石炭の調製方法。
［２］複数の石炭を混合してコークス製造用石炭を製造する際に、少なくとも一つの石炭について、該石炭の浸透距離を所定の値以下に調整してから混合することを特徴とするコークス製造用石炭の調製方法。
［３］前記石炭銘柄のギーセラー最高流動度を１００ｄｄｐｍ以上に調整することを特徴とする［１］または［２］に記載のコークス製造用石炭の調製方法。
［４］前記調製する石炭銘柄の浸透距離の所定の値を下記式（１）にて規定することを特徴とする［１］ないし［３］のいずれかに記載のコークス製造用石炭の調製方法。
浸透距離＝１．３×ａ×ｌｏｇＭＦｃ （１）
但し、ａは、ギーセラー最高流動度ＭＦの常用対数値ｌｏｇＭＦ＜２．５の範囲にある石炭の少なくとも１種以上の浸透距離及びｌｏｇＭＦを測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数であり、
ＭＦｃは、調製する石炭のギーセラー最高流動度（ｄｄｐｍ）である。
［５］前記ａが、１．７５＜ｌｏｇＭＦ＜２．５０の範囲にある石炭の少なくとも１種以上の浸透距離及びギーセラー最高流動度ＭＦの常用対数値ｌｏｇＭＦを測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数であることを特徴とする［４］に記載のコークス製造用石炭の調製方法。
［６］前記調製する石炭銘柄の浸透距離の所定の値を下記式（２）にて規定することを特徴とする［１］ないし［３］のいずれかに記載のコークス製造用石炭の調製方法。
浸透距離＝ａ’×ｌｏｇＭＦｃ＋ｂ （２）
但し、ａ’は、ギーセラー最高流動度ＭＦの常用対数値ｌｏｇＭＦ＜２．５の範囲にある石炭の少なくとも１種以上の浸透距離及びｌｏｇＭＦを測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数であり、
ｂは、前記回帰直線の作成に用いた銘柄から選ばれる１種類以上の同一試料を複数回測定した際の標準偏差の平均値以上で、前記平均値の５倍以下とする、定数であり、
ＭＦｃは、調製する石炭のギーセラー最高流動度（ｄｄｐｍ）である。
［７］前記ａ’は、１．７５＜ｌｏｇＭＦ＜２．５０の範囲にある石炭の少なくとも１種以上の浸透距離及びギーセラー最高流動度ＭＦの常用対数値ｌｏｇＭＦを測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数であることを特徴とする［６］に記載のコークス製造用石炭の調製方法。
［８］浸透距離の所定の値として、粒径２ｍｍ以下に調製した石炭を０．８ｇ／ｃｍ3の充填密度で容器内に厚さ１０ｍｍに充填して試料とし、該試料の上に直径２ｍｍのガラスビーズを配置し、該ガラスビーズの上部に５０ｋＰａの荷重を負荷しつつ、３℃／分の加熱速度で５５０℃まで前記試料を加熱する際に、前記ガラスビーズへ浸透した溶融試料の浸透距離の測定値で１５ｍｍとすることを特徴とする［１］ないし［３］のいずれかに記載のコークス製造用石炭の調製方法。
［９］配合炭を構成する複数種類の石炭の種類を予め決定し、それらの石炭の浸透距離の平均値に対して２倍以上の値を前記浸透距離の所定の値とすることを特徴とする、［１］ないし［３］のいずれかに記載のコークス製造用石炭の調製方法。
［１０］個別銘柄の石炭を調製する際に、産出場所の異なる複数種類の石炭を混合して、浸透距離を調整することを特徴とする［１］ないし［９］のいずれかに記載のコークス製造用石炭の調製方法。
［１１］石炭を、常温以上の温度で、Ｏ２、ＣＯ２、Ｈ２Ｏの１種以上の成分を含む雰囲気下に置く処理を行なうことで該石炭の浸透距離を低下させて調整することを特徴とする［１］ないし［９］のいずれかに記載のコークス製造用石炭の調製方法。
［１２］前記処理が、処理温度１００℃〜３００℃、処理時間１〜１２０分で行われる［１１］に記載のコークス製造用石炭の調製方法。
［１３］前記処理が、処理温度１８０℃〜２００℃、処理時間１〜３０分で行われる［１２］に記載のコークス製造用石炭の調製方法。 The features of the present invention for solving such problems are as follows.
[1] A coke characterized by adjusting the permeation distance of the brand coal to a predetermined value or less when preparing individual brand coal used alone or in combination with other coal as a raw material for producing coke. A method for preparing coal for production.
[2] Coke production characterized in that, when a plurality of coals are mixed to produce a coal for producing coke, the permeation distance of the coal is adjusted to a predetermined value or less with respect to at least one coal. Coal preparation method.
[3] The method for preparing coal for coke production according to [1] or [2], wherein the highest Guelseller fluidity of the coal brand is adjusted to 100 ddpm or more.
[4] The method for preparing coal for coke production according to any one of [1] to [3], wherein a predetermined value of a permeation distance of the coal brand to be prepared is defined by the following formula (1): .
Permeation distance = 1.3 × a × logMFc (1)
However, a measures the penetration distance and log MF of at least one kind of coal in the range of the common logarithm log MF <2.5 of the Gieseler maximum fluidity MF, and uses the measured value to calculate a regression line passing through the origin. A constant in the range of 0.7 to 1.0 times the coefficient of logMF at the time of creation,
MFc is the Gieseler maximum fluidity (ddpm) of the coal to be prepared.
[5] Measure the common logarithm log MF of at least one permeation distance of coal within the range of 1.75 <log MF <2.50 and the Gieseler maximum fluidity MF, using the measured value. The method for preparing coal for coke production according to [4], wherein the constant is in the range of 0.7 to 1.0 times the coefficient of log MF when a regression line passing through the origin is created.
[6] The method for preparing coal for coke production according to any one of [1] to [3], wherein a predetermined value of an infiltration distance of the coal brand to be prepared is defined by the following formula (2): .
Permeation distance = a ′ × logMFc + b (2)
However, a ′ is a regression line passing through the origin by measuring at least one permeation distance and log MF of coal in the range of logarithm log MF <2.5 of logarithm of the highest flow rate MF of Gieseer. Is a constant in the range of 0.7 to 1.0 times the coefficient of log MF when
b is a constant that is not less than the average value of the standard deviation when measuring one or more types of the same sample selected from the brands used to create the regression line, and not more than 5 times the average value,
MFc is the Gieseler maximum fluidity (ddpm) of the coal to be prepared.
[7] The above a ′ measures the common logarithm log MF of at least one permeation distance of coal in the range of 1.75 <log MF <2.50 and Gieseler maximum fluidity MF, and uses the measured value. The method for preparing coke-producing coal as described in [6], wherein the constant is in the range of 0.7 to 1.0 times the log MF coefficient when a regression line passing through the origin is created.
[8] As a predetermined value of the infiltration distance, coal prepared to a particle size of 2 mm or less is packed into a container with a packing density of 0.8 g / cm 3 to a thickness of 10 mm to form a sample, and a diameter of 2 mm is placed on the sample. When the sample is heated to 550 ° C. at a heating rate of 3 ° C./min while applying a load of 50 kPa on the top of the glass beads, the molten sample penetrated into the glass beads The method for preparing coal for coke production according to any one of [1] to [3], wherein a distance measurement value is 15 mm.
[9] A plurality of types of coal constituting the blended coal are determined in advance, and a value more than twice the average value of the penetration distance of the coal is set as the predetermined value of the penetration distance. The method for preparing coal for producing coke according to any one of [1] to [3].
[10] The coke according to any one of [1] to [9], wherein when preparing individual brand coal, a plurality of types of coal from different production locations are mixed to adjust the penetration distance A method for preparing coal for production.
[11] Adjusting by reducing the permeation distance of the coal by performing a process of placing the coal in an atmosphere containing one or more components of O 2 , CO 2 , and H 2 O at a temperature equal to or higher than normal temperature. The method for preparing coal for producing coke according to any one of [1] to [9].
[12] The method for preparing coal for coke production according to [11], wherein the treatment is performed at a treatment temperature of 100 ° C to 300 ° C and a treatment time of 1 to 120 minutes.
[13] The method for preparing coal for coke production according to [12], wherein the treatment is performed at a treatment temperature of 180 ° C. to 200 ° C. and a treatment time of 1 to 30 minutes.

本発明によれば、コークス炉内での石炭の軟化溶融層周辺に存在する欠陥構造、特に軟化溶融層に隣接するコークス層に存在する亀裂の影響を模擬し、また、コークス炉内での軟化溶融物周辺の拘束条件を適切に再現した状態での、石炭の軟化溶融特性の評価が可能な測定値、すなわち、欠陥構造への軟化溶融物浸透距離を用いることで、高強度の冶金用コークス製造に好適な原料石炭を調製することができる。   According to the present invention, the defect structure existing around the softening and melting layer of coal in the coke oven, particularly the effect of cracks existing in the coke layer adjacent to the softening and melting layer, is simulated, and the softening in the coke oven is performed. High-strength coke for metallurgical use by using the measured value that can evaluate the softening and melting characteristics of coal with the appropriate reproduction of restraint conditions around the melt, that is, the softened melt penetration distance into the defect structure. Raw material coal suitable for production can be prepared.

本発明で使用する試料と上下面に貫通孔を有する材料に一定荷重を負荷しつつ軟化溶融特性を測定する装置の一例を示す概略図である。It is the schematic which shows an example of the apparatus which measures a softening-melting characteristic, applying a fixed load to the sample used by this invention, and the material which has a through-hole in an upper and lower surface. 本発明で使用する上下面に貫通孔を有する材料のうち、円形貫通孔をもつものの一例を示す概略図である。It is the schematic which shows an example of what has a circular through-hole among the materials which have a through-hole in the upper and lower surfaces used by this invention. 本発明で使用する上下面に貫通孔を有する材料のうち、球形粒子充填層の一例を示す概略図である。It is the schematic which shows an example of a spherical particle packing layer among the materials which have a through-hole in the upper and lower surfaces used by this invention. 本発明で使用する上下面に貫通孔を有する材料のうち、円柱充填層の一例を示す概略図である。It is the schematic which shows an example of a cylindrical packing layer among the materials which have a through-hole in the upper and lower surfaces used by this invention. 石炭軟化溶融物の浸透距離の測定結果を示すグラフである。It is a graph which shows the measurement result of the penetration distance of a coal softening melt. 実施例１で使用したＡ炭及びＦ炭の浸透距離及び最高流動度と、（イ）に該当する浸透距離及び最高流動度の範囲との位置関係を示すグラフである。It is a graph which shows the positional relationship of the osmosis | permeation distance and the maximum fluidity of A charcoal and F charcoal which were used in Example 1, and the range of the osmosis | permeation distance and the maximum fluidity applicable to (A). 実施例１で使用したＡ炭及びＦ炭の浸透距離及び最高流動度と、（ロ）に該当する浸透距離及び最高流動度の範囲との位置関係を示すグラフである。It is a graph which shows the positional relationship with the osmosis | permeation distance and the maximum fluidity of A charcoal and F charcoal which were used in Example 1, and the range of the osmosis | permeation distance and the maximum fluidity applicable to (b). 本発明で使用する石炭試料と上下面に貫通孔を有する材料を一定容積に保ちつつ軟化溶融特性を測定する装置の一例を示す概略図である。It is the schematic which shows an example of the apparatus which measures a softening-melting characteristic, keeping the coal sample used by this invention, and the material which has a through-hole in an upper and lower surface at a fixed volume.

コークスは、一般に、様々な品位を持つ複数の銘柄を配合した配合炭を乾留して製造される。それぞれの銘柄の品位は、購買契約などに定められた基準の品位を満足するように産炭地において品位調整されて出荷されるのが通常である。その品位は産出される石炭の品位により制約を受けるが、同一炭鉱であっても産出場所や産出後の処理方法によりその品位は同一ではない。   Coke is generally produced by dry distillation of coal blended with a plurality of brands having various grades. Usually, the quality of each brand is shipped after being adjusted in the coal producing area so as to satisfy the standard quality defined in the purchase contract or the like. The quality is restricted by the quality of the coal produced, but even if it is the same coal mine, the quality is not the same depending on the production location and the processing method after production.

本発明者らは、新たな測定方法により測定可能となった、軟化溶融特性の新たな評価指標である「浸透距離」が、コークス強度を制御する上で従来の指標よりも優れた評価指標であることを見出した。そして、新たな評価方法により望ましいと判断される軟化溶融特性を持つ原料石炭銘柄の調製方法について検討を行なった結果、異なる性状の石炭を組み合わせたり、石炭に好適な事前処理を行なったりすることで望ましい性状の石炭が調製可能であることを見出し、本発明の完成に至った。「浸透距離」の測定は、概略以下のようにして行なうことができる。   The present inventors are able to measure by a new measuring method, and the “penetration distance”, which is a new evaluation index of softening and melting characteristics, is an evaluation index superior to the conventional index in controlling coke strength. I found out. And as a result of examining the preparation method of the raw material coal brand with softening and melting characteristics judged to be desirable by the new evaluation method, it is possible to combine coals with different properties or perform pretreatment suitable for coal. It has been found that coal having desirable properties can be prepared, and the present invention has been completed. The “penetration distance” can be measured as follows.

図１に本発明で使用する軟化溶融特性（浸透距離）の測定装置の一例を示す。図１は石炭試料と上下面に貫通孔を有する材料に一定荷重を負荷させて石炭試料を加熱する場合の装置である。容器３下部に石炭を充填して試料１とし、試料１の上に、上下面に貫通孔を有する材料２を配置する。試料１を軟化溶融開始温度以上に加熱し、上下面に貫通孔を有する材料２に試料を浸透させ、浸透距離を測定するものである。加熱は不活性ガス雰囲気下で行なう。ここで、不活性ガスとは、測定温度域で石炭と反応しないガスを指し、代表的なガスとしてはアルゴンガス、ヘリウムガス、窒素ガス等である。なお、浸透距離の測定は、石炭と貫通孔を有する材料を一定容積に保ちつつ加熱するようにしてもよい。その場合に使用する軟化溶融特性（浸透距離）の測定装置の一例を図８に示す。   FIG. 1 shows an example of a measuring device for softening and melting characteristics (penetration distance) used in the present invention. FIG. 1 shows an apparatus for heating a coal sample by applying a constant load to the coal sample and a material having through holes on the upper and lower surfaces. The lower part of the container 3 is filled with coal to form a sample 1, and a material 2 having through holes on the upper and lower surfaces is arranged on the sample 1. The sample 1 is heated to the softening and melting start temperature or higher, the sample is permeated into the material 2 having through holes on the upper and lower surfaces, and the permeation distance is measured. Heating is performed in an inert gas atmosphere. Here, the inert gas refers to a gas that does not react with coal in the measurement temperature range, and representative gases include argon gas, helium gas, nitrogen gas, and the like. Note that the penetration distance may be measured by heating the material having coal and the through-holes while maintaining a constant volume. An example of a measuring device for softening and melting characteristics (penetration distance) used in that case is shown in FIG.

図１に示す試料１と上下面に貫通孔を有する材料２に一定荷重を負荷して試料１を加熱する場合、試料１が膨張又は収縮を示し、上下面に貫通孔を有する材料２が上下方向に移動する。よって、上下面に貫通孔を有する材料２を介して試料浸透時の膨張率を測定することが可能である。図１に示すように上下面に貫通孔を有する材料２の上面に膨張率検出棒１３を配置し、膨張率検出棒１３の上端に荷重付加用の錘１４を乗せ、その上に変位計１５を配置し、膨張率を測定する。変位計１５は、試料の膨張率の膨張範囲（−１００％〜３００％）を測定可能なものを用いれば良い。加熱系内を不活性ガス雰囲気に保持する必要があるため、非接触式の変位計が適しており、光学式変位計を用いることが望ましい。不活性ガス雰囲気としては、窒素雰囲気とすることが好ましい。上下面に貫通孔を有する材料２が粒子充填層の場合は、膨張率検出棒１３が粒子充填層に埋没する可能性があるため、上下面に貫通孔を有する材料２と膨張率検出棒１３の間に板を挟む措置を講ずるのが望ましい。負荷させる荷重は、試料上面に配置した上下面に貫通孔を有する材料の上面に対して、均等にかけることが好ましく、上下面に貫通孔を有する材料の上面の面積に対し、５〜８０ｋＰａ、好ましくは１５〜５５ｋＰａ、最も好ましくは２５〜５０ｋＰａの圧力を負荷することが望ましい。この圧力は、コークス炉内における軟化溶融層の膨張圧に基づいて設定することが好ましいが、測定結果の再現性、種々の石炭での銘柄差の検出力を検討した結果、炉内の膨張圧よりはやや高めの２５〜５０ｋＰａ程度が測定条件として最も好ましいことを見出した。   When a constant load is applied to the sample 1 shown in FIG. 1 and the material 2 having through holes on the upper and lower surfaces and the sample 1 is heated, the sample 1 expands or contracts, and the material 2 having the through holes on the upper and lower surfaces Move in the direction. Therefore, it is possible to measure the expansion coefficient at the time of sample penetration through the material 2 having through holes on the upper and lower surfaces. As shown in FIG. 1, an expansion coefficient detecting rod 13 is arranged on the upper surface of a material 2 having through holes on the upper and lower surfaces, a weight 14 for applying a load is placed on the upper end of the expansion coefficient detecting rod 13, and a displacement meter 15 is placed thereon. And measure the expansion rate. The displacement meter 15 may be one that can measure the expansion range (-100% to 300%) of the expansion coefficient of the sample. Since it is necessary to maintain the inside of the heating system in an inert gas atmosphere, a non-contact type displacement meter is suitable, and it is desirable to use an optical displacement meter. The inert gas atmosphere is preferably a nitrogen atmosphere. In the case where the material 2 having through holes on the upper and lower surfaces is a particle packed layer, the expansion coefficient detecting rod 13 may be buried in the particle packed layer, and therefore the material 2 having the through holes on the upper and lower surfaces and the expansion coefficient detecting rod 13. It is desirable to take measures to sandwich the board between the two. The load to be applied is preferably evenly applied to the upper surface of the material having through holes on the upper and lower surfaces arranged on the upper surface of the sample, and 5 to 80 kPa with respect to the area of the upper surface of the material having the through holes on the upper and lower surfaces, It is desirable to apply a pressure of preferably 15 to 55 kPa, most preferably 25 to 50 kPa. This pressure is preferably set based on the expansion pressure of the softened and molten layer in the coke oven, but as a result of examining the reproducibility of the measurement results and the ability to detect the difference in brands in various coals, It has been found that a slightly higher level of about 25 to 50 kPa is most preferable as a measurement condition.

加熱手段は、試料の温度を測定しつつ、所定の昇温速度で加熱できる方式のものを用いることが望ましい。具体的には、電気炉や、導電性の容器と高周波誘導を組み合わせた外熱式、またはマイクロ波のような内部加熱式である。内部加熱式を採用する場合は、試料内温度を均一にする工夫を施す必要があり、例えば、容器の断熱性を高める措置を講ずることが好ましい。   It is desirable to use a heating means that can heat at a predetermined rate of temperature rise while measuring the temperature of the sample. Specifically, an electric furnace, an external heating type that combines a conductive container and high frequency induction, or an internal heating type such as a microwave. When the internal heating method is adopted, it is necessary to devise a method for making the temperature in the sample uniform, and for example, it is preferable to take measures to increase the heat insulation of the container.

加熱速度については、コークス炉内での石炭及び粘結材の軟化溶融挙動を模擬するという目的から、コークス炉内での石炭の加熱速度に一致させる必要がある。コークス炉内での軟化溶融温度域における石炭の加熱速度は炉内の位置や操業条件によって異なるが概ね２〜１０℃／分であり、平均的な加熱速度として２〜４℃／分とすることが望ましく、もっとも望ましいのは３℃／分程度である。しかし、非微粘結炭のように流動性の低い石炭の場合、３℃／分では浸透距離や膨張が小さく、検出が困難となる可能性がある。石炭は急速加熱することによりギーセラープラストメータによる流動性が向上することが一般的に知られている。従って、例えば浸透距離が１ｍｍ以下の石炭の場合には、検出感度を向上させるために、加熱速度を１０〜１０００℃／分に高めて測定しても良い。   The heating rate needs to match the heating rate of coal in the coke oven for the purpose of simulating the softening and melting behavior of coal and binder in the coke oven. Although the heating rate of coal in the softening and melting temperature range in the coke oven varies depending on the position in the furnace and operating conditions, it is generally 2 to 10 ° C / min, and the average heating rate should be 2 to 4 ° C / min. The most desirable is about 3 ° C./min. However, in the case of coal with low fluidity such as non-slightly caking coal, the permeation distance and expansion are small at 3 ° C./min, which may make detection difficult. It is generally known that coal is improved in fluidity by a Gisela plastometer by rapid heating. Therefore, for example, in the case of coal with an infiltration distance of 1 mm or less, measurement may be performed with the heating rate increased to 10 to 1000 ° C./min in order to improve detection sensitivity.

加熱を行なう温度範囲については、石炭及び粘結材の軟化溶融特性の評価が目的であるため、石炭及び粘結材の軟化溶融温度域まで加熱できればよい。コークス製造用の石炭及び粘結材の軟化溶融温度域を考慮すると、０℃（室温）〜５５０℃の範囲において、好ましくは石炭の軟化溶融温度である３００〜５５０℃の範囲で所定の加熱速度で加熱すればよい。   About the temperature range which heats, since the objective is evaluation of the softening and melting characteristic of coal and a binder, what is necessary is just to be able to heat to the softening and melting temperature range of coal and a binder. Considering the softening and melting temperature range of coal and caking material for coke production, a predetermined heating rate in the range of 0 ° C (room temperature) to 550 ° C, preferably in the range of 300 to 550 ° C, which is the softening and melting temperature of coal. You can heat with.

上下面に貫通孔を有する材料は、透過係数をあらかじめ測定または算出できるものが望ましい。材料の形態の例として、貫通孔を持つ一体型の材料、粒子充填層が挙げられる。貫通孔を持つ一体型の材料としては、例えば、図２に示すような円形の貫通孔１６を持つもの、矩形の貫通孔を持つもの、不定形の貫通孔を持つものなどが挙げられる。粒子充填層としては、大きく球形粒子充填層、非球形粒子充填層に分けられ、球形粒子充填層としては図３に示すようなビーズの充填粒子１７からなるもの、非球形粒子充填層としては不定形粒子や、図４に示すような充填円柱１８からなるものなどが挙げられる。測定の再現性を保つため、材料内の透過係数はなるべく均一で、かつ測定を簡便にするため、透過係数の算出が容易なものが望ましい。したがって、本発明で用いる上下面に貫通孔を有する材料には球形粒子充填層の利用が特に望ましい。上下面に貫通孔を有する材料の材質は、石炭軟化溶融温度域以上、具体的には６００℃まで形状がほとんど変化せず、石炭とも反応しないものならば特に指定はない。また、その高さは、石炭の溶融物が浸透するのに十分な高さがあればよく、厚み５〜２０ｍｍの石炭層を加熱する場合には、２０〜１００ｍｍ程度あればよい。   The material having through holes on the upper and lower surfaces is preferably one that can measure or calculate the transmission coefficient in advance. Examples of the form of the material include an integrated material having a through hole and a particle packed layer. Examples of the integrated material having a through hole include a material having a circular through hole 16 as shown in FIG. 2, a material having a rectangular through hole, and a material having an indeterminate shape. The particle packed layer is roughly divided into a spherical particle packed layer and a non-spherical particle packed layer. The spherical particle packed layer is composed of beads packed particles 17 as shown in FIG. 3, and the non-spherical particle packed layer is not suitable. Examples thereof include regular particles and those made of filled cylinders 18 as shown in FIG. In order to maintain the reproducibility of the measurement, it is desirable that the transmission coefficient in the material is as uniform as possible and that the calculation of the transmission coefficient is easy in order to simplify the measurement. Therefore, the use of a spherical particle packed bed is particularly desirable for the material having through holes on the upper and lower surfaces used in the present invention. The material having the through holes on the upper and lower surfaces is not particularly specified as long as the shape hardly changes to the coal softening and melting temperature range, specifically up to 600 ° C., and does not react with coal. Moreover, the height should just be sufficient height for the melt of coal to osmose | permeate, and what is necessary is just about 20-100 mm when heating a coal layer of thickness 5-20 mm.

上下面に貫通孔を有する材料の透過係数は、コークス層に存在する粗大欠陥の透過係数を推定して設定する必要がある。本発明に特に望ましい透過係数について、粗大欠陥構成因子の考察や大きさの推定など、本発明者らが検討を重ねた結果、透過係数が１×１０8〜２×１０9ｍ-2の場合が最適であることを見出した。この透過係数は、下記（３）式で表されるＤａｒｃｙ則に基づき導出されるものである。
ΔＰ／Ｌ＝Ｋ・μ・ｕ ・・・ （３）
ここで、ΔＰは上下面に貫通孔を有する材料内での圧力損失［Ｐａ］、Ｌは貫通孔を有する材料の高さ［ｍ］、Ｋは透過係数［ｍ-2］、μは流体の粘度［Ｐａ・ｓ］、ｕは流体の速度［ｍ／ｓ］である。例えば上下面に貫通孔を有する材料として均一な粒径のガラスビーズ層を用いる場合、上述の好適な透過係数を持つようにするためには、直径０．２ｍｍから３．５ｍｍ程度のガラスビーズを選択することが望ましく、もっとも望ましいのは２ｍｍである。 The transmission coefficient of the material having through holes on the upper and lower surfaces needs to be set by estimating the transmission coefficient of coarse defects present in the coke layer. In the case where the transmission coefficient is 1 × 10 8 to 2 × 10 9 m −2 as a result of repeated investigations by the present inventors, such as consideration of coarse defect constituent factors and estimation of the size, which are particularly desirable for the present invention. Was found to be optimal. This transmission coefficient is derived based on the Darcy rule expressed by the following equation (3).
ΔP / L = K · μ · u (3)
Here, ΔP is the pressure loss [Pa] in the material having through holes on the upper and lower surfaces, L is the height [m] of the material having the through holes, K is the transmission coefficient [m −2 ], μ is the fluid. Viscosity [Pa · s], u is fluid velocity [m / s]. For example, when a glass bead layer having a uniform particle diameter is used as a material having through holes on the upper and lower surfaces, in order to have the above-mentioned preferable transmission coefficient, glass beads having a diameter of about 0.2 mm to 3.5 mm are used. It is desirable to choose, most preferably 2 mm.

測定試料とする石炭および粘結材はあらかじめ粉砕し、所定の充填密度で所定の層厚に充填する。粉砕粒度としては、コークス炉における装入石炭の粒度（粒径３ｍｍ以下の粒子の比率が全体の７０〜８０質量％程度）としてもよく、粒径３ｍｍ以下が７０質量％以上となるように粉砕することが好ましいが、小さい装置での測定であることを考慮して、全量を粒径２ｍｍ以下に粉砕した粉砕物を用いることが特に好ましい。粉砕物を充填する密度はコークス炉内の充填密度に合わせ０．７〜０．９ｇ／ｃｍ3とすることができるが、再現性、検出力を検討した結果、０．８ｇ／ｃｍ3が好ましいことを知見した。また、充填する層厚は、コークス炉内における軟化溶融層の厚みに基づいて層厚５〜２０ｍｍとすることができるが、再現性、検出力を検討した結果、層厚は１０ｍｍとすることが好ましいことを知見した。
以上の浸透距離の測定において、代表的な測定条件を以下に記す。
（１）石炭又は粘結材を粒径２ｍｍ以下が１００質量％となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．８ｇ／ｃｍ３で、層厚が１０ｍｍとなるように容器に充填して試料を作成し、
（２）該試料の上に直径２ｍｍのガラスビーズを浸透距離以上の厚さ（通常は層厚８０ｍｍ）となるように配置し、
（３）前記ガラスビーズの上部から５０ｋＰａとなるように荷重を負荷しつつ、加熱速度３℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱し、
（４）前記ガラスビーズ層へ浸透した溶融試料の浸透距離を測定する。 The coal and binder used as the measurement sample are pulverized in advance and filled to a predetermined layer thickness with a predetermined packing density. The pulverized particle size may be the particle size of the coal charged in the coke oven (the ratio of particles having a particle size of 3 mm or less is about 70 to 80% by mass), and pulverization is performed so that the particle size of 3 mm or less is 70% by mass or more. However, it is particularly preferable to use a pulverized product in which the total amount is pulverized to a particle size of 2 mm or less in consideration of measurement with a small apparatus. The density for filling the pulverized product can be 0.7 to 0.9 g / cm 3 in accordance with the packing density in the coke oven. As a result of studying reproducibility and detection power, 0.8 g / cm 3 is preferable. I found out. Further, the layer thickness to be filled can be 5 to 20 mm based on the thickness of the softened and melted layer in the coke oven, but as a result of studying reproducibility and detection power, the layer thickness should be 10 mm. I found it preferable.
In the measurement of the above penetration distance, typical measurement conditions are described below.
(1) Coal or caking material is pulverized so that the particle size of 2 mm or less is 100% by mass, and the pulverized coal or caking material has a packing density of 0.8 g / cm 3 and a layer thickness of 10 mm. Create a sample by filling the container like
(2) A glass bead having a diameter of 2 mm is disposed on the sample so as to have a thickness equal to or greater than the permeation distance (usually a thickness of 80 mm)
(3) Heating in an inert gas atmosphere from room temperature to 550 ° C. at a heating rate of 3 ° C./min while applying a load from the top of the glass beads to 50 kPa,
(4) The penetration distance of the molten sample that has penetrated into the glass bead layer is measured.

石炭及び粘結材の軟化溶融物の浸透距離は、加熱中に常時連続的に測定できることが本来望ましい。しかし、常時測定は、試料から発生するタールの影響などにより、困難である。加熱による石炭の膨張、浸透現象は不可逆的であり、一旦膨張、浸透した後は冷却してもほぼその形状が保たれているので、石炭溶融物が浸透終了した後、容器全体を冷却し、冷却後の浸透距離を測定することで加熱中にどこまで浸透したかを測定するようにしてもよい。例えば、冷却後の容器から上下面に貫通孔を有する材料を取り出し、ノギスや定規で直接測定することが可能である。また、上下面に貫通孔を有する材料として粒子を使用した場合には、粒子間空隙に浸透した軟化溶融物は、浸透した部分までの粒子層全体を固着させている。したがって、前もって粒子充填層の質量と高さの関係を求めておけば、浸透終了後、固着していない粒子の質量を測定し、初期質量から差し引くことで、固着している粒子の質量を導出でき、そこから浸透距離を算出することができる。   It is inherently desirable that the penetration distance of the softened melt of coal and caking can be measured continuously during heating. However, continuous measurement is difficult due to the influence of tar generated from the sample. The expansion and infiltration phenomenon of coal by heating is irreversible, and once expanded and infiltrated, the shape is maintained even after cooling, so after the coal melt has been infiltrated, the entire container is cooled, You may make it measure how much it penetrate | infiltrated during the heating by measuring the penetration distance after cooling. For example, it is possible to take out a material having through holes on the upper and lower surfaces from the cooled container and directly measure with a caliper or a ruler. Further, when particles are used as the material having through holes on the upper and lower surfaces, the softened melt that has permeated the interparticle voids fixes the entire particle layer up to the permeated portion. Therefore, if the relationship between the mass and height of the particle packed bed is obtained in advance, the mass of the non-adhered particles is measured after the infiltration, and the mass of the adhering particles is derived by subtracting from the initial mass. And the penetration distance can be calculated therefrom.

このような浸透距離の優位性は、コークス炉内状況に近い測定方法をとることに基づいて原理的に想定されるだけではなく、コークス強度への浸透距離の影響を調査した結果からも明らかとなった。実際、本発明の評価方法により、同程度のｌｏｇＭＦ（ギーセラープラストメータ法による最高流動度の常用対数値）を持つ石炭であっても、銘柄により浸透距離に差があることが明らかとなり、浸透距離の異なる石炭を配合してコークスを製造した場合のコークス強度に対する影響も異なることが確認された。   The superiority of such penetration distance is not only assumed in principle based on the measurement method close to the coke oven conditions, but is also clear from the results of investigating the effect of penetration distance on coke strength. became. In fact, according to the evaluation method of the present invention, even if the coal has the same log MF (the common logarithm of the maximum fluidity by the Gieseller Plastometer method), it is clear that there is a difference in the penetration distance depending on the brand. It was confirmed that the effect on coke strength when coke was produced by blending coal with different distances was also different.

従来のギーセラープラストメータによる軟化溶融特性の評価では、高い流動性を示す石炭の方が石炭粒子同士を接着する効果が高いと考えられてきた。一方で、浸透距離とコークス強度との関係を調査することで、極端に浸透距離の大きい石炭を配合するとコークス化時に粗大な欠陥を残し、かつ薄い気孔壁の組織構造を形成するため、コークス強度が配合炭の平均品位から予想される値に比べて低下することが分かった。これは、浸透距離が大きすぎる石炭は、周囲の石炭粒子間に顕著に浸透することで、その石炭粒子が存在していた部分自体が大きな空洞となり、欠陥となってしまうためと推測される。特にギーセラープラストメータによる軟化溶融特性の評価において高い流動性を示す石炭においては、浸透距離の大小によりコークス中に残存する粗大な欠陥の生成量が異なることが分かった。この関係は粘結材に関しても同様に見られた。   In the evaluation of the softening and melting characteristics using a conventional Gieseller plastometer, it has been considered that coal exhibiting high fluidity has a higher effect of adhering coal particles. On the other hand, by investigating the relationship between permeation distance and coke strength, when coal with extremely large permeation distance is blended, coarse defects are left at the time of coking and a thin pore wall structure is formed. Was found to be lower than the value expected from the average quality of the blended coal. This is presumed to be because coal with a too long permeation distance permeates significantly between surrounding coal particles, so that the portion where the coal particles existed itself becomes a large cavity and becomes a defect. In particular, in the evaluation of softening and melting characteristics with a Gieseler plastometer, it was found that the amount of coarse defects remaining in the coke differs depending on the penetration distance in coal that exhibits high fluidity. This relationship was similarly observed for the binder.

本発明者らが鋭意研究を重ねた結果、コークス製造用原料に配合して使用される際に、コークス強度の低下を招く石炭ないし粘結材の浸透距離の範囲は、以下の（イ）〜（ニ）の４通りで規定することが効果的であることを見出した。   As a result of intensive studies by the present inventors, the range of the penetration distance of coal or caking additive that causes a reduction in coke strength when used in a coke production raw material is as follows. It was found that it is effective to prescribe in the four ways of (d).

（イ）浸透距離の範囲を、下記式にて規定する。
浸透距離＞１．３×ａ×ｌｏｇＭＦｃ
但しａは、ｌｏｇＭＦ＜２．５の範囲にある石炭及び粘結材の少なくとも１種以上の浸透距離及びｌｏｇＭＦを測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数である。ＭＦｃは、浸透距離の範囲を判断しようとする石炭のギーセラー最高流動度（ｄｄｐｍ）である。 (B) The range of penetration distance is defined by the following formula.
Permeation distance> 1.3 x a x logMFc
However, a is the log MF of log MF when measuring the penetration distance and log MF of at least one kind of coal and binder in the range of log MF <2.5, and creating a regression line passing through the origin using the measured value. It is a constant in the range of 0.7 to 1.0 times the coefficient. MFc is the coal gheseler maximum fluidity (ddpm) to determine the range of penetration distance.

（ロ）浸透距離の範囲を、下記式にて規定する。
浸透距離＞ａ’×ｌｏｇＭＦｃ＋ｂ
但しａ’は、ｌｏｇＭＦ＜２．５の範囲にある石炭及び粘結材の少なくとも１種以上の浸透距離及び最高流動度を測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数である。ｂは、前記回帰直線の作成に用いた銘柄から選ばれる１種類以上の同一試料を複数回測定した際の標準偏差の平均値以上で、前記平均値の５倍以下とする、定数である。ＭＦｃは、浸透距離の範囲を判断しようとする石炭のギーセラー最高流動度（ｄｄｐｍ）である。 (B) The range of penetration distance is defined by the following formula.
Permeation distance> a ′ × logMFc + b
However, when a ′ is measured, the penetration distance and the maximum fluidity of at least one kind of coal and binder in the range of log MF <2.5 are measured, and a regression line passing through the origin is created using the measured values. Is a constant in the range of 0.7 to 1.0 times the coefficient of log MF. b is a constant that is not less than the average value of the standard deviation when measuring one or more types of the same sample selected from the brands used for creating the regression line, and not more than 5 times the average value. MFc is the coal gheseler maximum fluidity (ddpm) to determine the range of penetration distance.

（ハ）コークス製造に用いる配合炭の銘柄が予め決定できる場合には、配合炭に含まれる石炭の浸透距離の単純平均値に対して２倍超え。   (C) When the brand name of the coal blend used for coke production can be determined in advance, it exceeds twice the simple average value of the penetration distance of coal contained in the coal blend.

（ニ）粒径２ｍｍ以下、１００ｍａｓｓ％の粒度に調製した石炭試料を０．８ｇ／ｃｍ3の充填密度で容器内に厚さ１０ｍｍに充填し、貫通孔を有する材料として直径２ｍｍのガラスビーズを用い、５０ｋPaの荷重をかけ、３℃/分の加熱速度で５５０℃まで加熱して測定した場合、浸透距離１５ｍｍ超え。 (D) A coal sample prepared to have a particle size of 2 mm or less and a particle size of 100 mass% is filled in a container with a packing density of 0.8 g / cm 3 to a thickness of 10 mm, and glass beads having a diameter of 2 mm are used as materials having through holes. When using a 50 kPa load and heating to 550 ° C. at a heating rate of 3 ° C./min, the penetration distance exceeds 15 mm.

ここで、上記（イ）〜（ニ）の４種類の管理値の決め方を示したのは、浸透距離の値は、設定された測定条件、例えば、荷重、昇温速度、貫通孔を有する材料の種類、装置の構成、等によって変化するためで、本発明で述べた例と異なる測定条件の場合があることを考慮して検討した結果、（イ）〜（ハ）のような管理値の決め方が有効であることを見出したことに基づくものである。   Here, the method of determining the four types of management values (i) to (d) described above is that the value of the permeation distance is a material having a set measurement condition, for example, a load, a heating rate, and a through hole. As a result of considering that there are cases where the measurement conditions differ from the example described in the present invention, the management values of (a) to (c) are changed. This is based on the finding that the decision method is effective.

また、（イ）、（ロ）の範囲を決める際に使用する式の定数ａおよびａ’は、ｌｏｇＭＦ＜２．５の範囲にある石炭の少なくとも１つ以上の浸透距離及び最高流動度を測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲となるように定める。これは、ｌｏｇＭＦ＜２．５の範囲では、石炭の最高流動度と浸透距離の間にはほぼ正の相関が見られるが、強度低下を招く銘柄は、その浸透距離がこの相関から正に大きく偏倚している銘柄であるためである。本発明者らは、鋭意検討を重ねた結果、上記回帰式により石炭のｌｏｇＭＦ値に応じて求めた浸透距離の１．３倍以上の範囲に該当する銘柄が、強度低下を招く銘柄であることを知見し、（イ）のように範囲の規定を行うこととした。また、上記回帰式から、測定誤差を超えて正に偏倚する銘柄を検出するべく、上記回帰式に、同一試料を複数回測定した際の標準偏差の１〜５倍を加えた値以上の範囲に該当する銘柄が、強度低下を招く銘柄であることを知見し、（ロ）のように範囲の規定を行うこととした。従って、定数ｂは、同一試料を複数回測定した際の標準偏差の１〜５倍の値を用いれば良く、本発明で述べた測定条件の場合、０．６〜３．０ｍｍ程度である。この時、どちらの式とも、その石炭のｌｏｇＭＦ値に基づいて強度低下を招く浸透距離の範囲を定めている。これは、ＭＦが大きいほど一般に浸透距離が高くなるため、その相関からどの程度偏倚するかが重要であるためである。なお、回帰直線の作成には、公知の最小二乗法による直線回帰の方法を用いてもよい。回帰の際に用いる石炭の数は多いほど回帰の誤差が少なくなるので好ましい。特に、ＭＦが小さい銘柄では浸透距離が小さく誤差が大きくなりやすいため、１．７５＜ｌｏｇＭＦ＜２．５０の範囲にある石炭の１種以上を用いて回帰直線を求めることが特に好ましい。   In addition, the constants a and a ′ used in determining the ranges of (A) and (B) measure at least one penetration distance and maximum fluidity of coal in the range of logMF <2.5. Then, it is determined to be within a range of 0.7 to 1.0 times the log MF coefficient when a regression line passing through the origin is created using the measured value. This is because, in the range of log MF <2.5, there is an almost positive correlation between the maximum coal flow rate and the penetration distance. This is because the brand is biased. As a result of intensive studies, the present inventors have a brand that falls within a range of 1.3 times or more the penetration distance determined according to the log MF value of coal according to the above regression equation, which leads to a decrease in strength. As a result, it was decided to define the range as shown in (a). In addition, from the above regression equation, in order to detect brands that deviate positively beyond the measurement error, a range equal to or greater than the value obtained by adding 1 to 5 times the standard deviation when the same sample is measured multiple times to the above regression equation. It was found that the brands that correspond to the brands that lead to a decrease in strength, and the range was defined as shown in (b). Accordingly, the constant b may be 1 to 5 times the standard deviation when the same sample is measured a plurality of times, and is about 0.6 to 3.0 mm under the measurement conditions described in the present invention. At this time, in both equations, the range of the penetration distance that causes the strength reduction is determined based on the log MF value of the coal. This is because, as the MF increases, the penetration distance generally increases, so how much deviation is important from the correlation. In addition, you may use the method of the linear regression by the well-known least square method for preparation of a regression line. The larger the number of coals used in the regression, the better the error in the regression. In particular, for brands with small MF, the penetration distance is small and the error tends to be large, so it is particularly preferable to obtain a regression line using one or more kinds of coal in the range of 1.75 <log MF <2.50.

ここで、定数ａおよびａ’、ｂともに範囲を規定しているのは、これらの値を減少させることで、強度低下を招く石炭がより確実に検出できるようになるためであり、その値は操業上の要求によって調整することができる。ただし、この値を小さくしすぎると、コークス強度に悪影響を及ぼすと推定される石炭が多くなりすぎることおよび、実際は強度低下を招かない石炭であっても強度低下を起こすと誤認してしまうという問題が生じてしまうため、ａおよびａ’については回帰直線の傾きの０．７〜１．０倍とすることが好ましく、また、ｂについては同一試料を複数回測定した際の標準偏差の１〜５倍とすることが好ましい。   Here, the reason why both the constants a and a ′ and b define the range is that by reducing these values, it is possible to more reliably detect coal that causes a decrease in strength. Can be adjusted according to operational requirements. However, if this value is too small, there will be too much coal estimated to have an adverse effect on coke strength, and it will be misunderstood that even coal that does not actually cause strength reduction will cause strength reduction. Therefore, a and a ′ are preferably 0.7 to 1.0 times the slope of the regression line, and b is 1 to 1 of the standard deviation when the same sample is measured a plurality of times. 5 times is preferable.

上記（イ）〜（ニ）に示した範囲に該当する浸透距離の値を有する石炭は、コークスの原料石炭（原料炭）として通常の操作により使用すると、コークス化の際に粗大な欠陥を残し、かつ薄い気孔壁の組織構造を形成するため、コークス強度の低下を招く。そのため、なるべく個々の石炭銘柄の浸透距離を上記管理値よりも小さくなるように調製し、そのような石炭をなるべく多く使用することがコークス強度を維持するための手段として簡便かつ有効である。   Coal having a permeation distance value corresponding to the range shown in (i) to (d) above will leave coarse defects during coking when used as a coke raw material coal (coking coal) by ordinary operations. In addition, since a thin pore wall structure is formed, coke strength is reduced. Therefore, it is convenient and effective as a means for maintaining the coke strength to adjust the permeation distance of each individual coal brand as much as possible and to use as much of such coal as possible.

上記のような望ましい特性を有する単一銘柄の原料炭を調製する方法としては、浸透距離の異なる石炭を混合することが最も容易である。本発明者らは、異なる品質の石炭を混合した場合の浸透距離について調査した結果、それぞれの石炭の浸透距離測定値を、それぞれの石炭の混合比率で加重平均した値と、配合炭の浸透距離測定値が概略一致することを見出し、原料炭の浸透距離を調整する方法を確立した。ただし、加重平均値と実測値には不可避的に存在する値のバラツキがあるので、最終的には配合炭の浸透距離の実測を行いその値をもってその配合炭の浸透距離とすることが望ましく、もし、実測された浸透距離が、本発明の範囲から外れる場合には、浸透距離の小さい銘柄を追加配合したり、可能であれば浸透距離の大きい銘柄の配合率を低下させたりすることで浸透距離を制御できる。   As a method for preparing a single brand of coking coal having desirable characteristics as described above, it is easiest to mix coal having different penetration distances. As a result of investigating the permeation distance when coals of different qualities are mixed, the inventors of the present invention obtained a weighted average value of each coal permeation distance measurement value by the mixing ratio of each coal and the permeation distance of the blended coal. We found that the measured values almost coincided, and established a method to adjust the penetration distance of coking coal. However, since there are variations in the values that inevitably exist in the weighted average value and the actual measurement value, it is desirable to finally measure the penetration distance of the blended coal and use that value as the penetration distance of the blended coal, If the measured penetration distance is out of the scope of the present invention, the addition of a brand with a small penetration distance or, if possible, the blending ratio of a brand with a large penetration distance is reduced. You can control the distance.

また、石炭の浸透距離は、石炭を空気中で加熱処理したり、常温であっても長時間放置したりすることで低下させて、調整することができる。このような処理は石炭の酸化もしくは風化と呼ばれる処理であるが、温度や時間、酸素含有量などの酸化条件を制御することによって酸化の程度を変えることで原料炭の浸透距離を低下させることができる。従来、石炭の酸化は粘結性の低下をもたらす現象として好ましくないものと認識されていたが、浸透距離という新物性を用いると、好適な酸化の程度の判断が可能になり、酸化の程度を制御することによって、石炭の品位を向上させうることが見出された点は本発明の大きな特徴である。また、酸素が存在しない雰囲気であっても、２５０℃以上の加熱処理によって浸透距離を低下可能であることも見出された。   Moreover, the penetration distance of coal can be adjusted by decreasing the heat treatment of the coal in air or by leaving it at room temperature for a long time. Such treatment is a treatment called oxidation or weathering of coal, but it can reduce the permeation distance of raw coal by changing the degree of oxidation by controlling the oxidation conditions such as temperature, time and oxygen content. it can. Conventionally, oxidation of coal has been recognized as an unfavorable phenomenon that causes a decrease in caking properties, but the use of a new physical property called permeation distance makes it possible to determine a suitable degree of oxidation and to reduce the degree of oxidation. It is a great feature of the present invention that it has been found that the quality of coal can be improved by controlling. It has also been found that the permeation distance can be reduced by heat treatment at 250 ° C. or higher even in an oxygen-free atmosphere.

石炭の風化の進行速度は、酸素濃度、圧力（気圧）、温度、石炭粒径、石炭水分等に依存することが一般的に知られている。浸透距離及び最高流動度の値を制御するために石炭を風化させるに際しては、上記の風化要因を適宜制御すればよい。   It is generally known that the speed of coal weathering depends on oxygen concentration, pressure (atmospheric pressure), temperature, coal particle size, coal moisture, and the like. When the coal is weathered in order to control the permeation distance and the maximum fluidity, the above-mentioned weathering factors may be appropriately controlled.

本発明者らは、上記の風化要因を変えて石炭を風化させる実験を行なうことによって、浸透距離及び最高流動度の低下速度が風化条件によって異なる事を知見した。以下、その具体的な方法について記述する。   The inventors of the present invention have found that the permeation distance and the rate of decrease in the maximum fluidity differ depending on the weathering conditions by conducting an experiment in which coal is weathered by changing the above-mentioned weathering factors. The specific method will be described below.

風化を行う際の雰囲気としては、酸化雰囲気である必要がある。ここで酸化雰囲気とは、酸素を含む、ないし酸素を解離し、酸化する能力を有する物質を含む雰囲気である。そのような条件は無数に存在するが、入手・制御の容易さを考慮すると、Ｏ２、ＣＯ２、Ｈ２Ｏを含む気体雰囲気が望ましい。気体雰囲気であれば、酸化力を酸化性ガスの濃度、圧力で容易に調整可能であり、また、処理後に不活性ガスと置換することで、石炭及び粘結材の酸化の進行を速やかに制止できるため、処理時間も任意に設定できる。ここで、酸化性ガスの濃度が高いほど、圧力が高いほど、風化の進行が早い。一方、酸化性の液体雰囲気の場合、風化処理後に石炭及び粘結材と速やかに分離するのが困難であり、風化の進行度を制御する上で好ましくない。 The atmosphere for weathering needs to be an oxidizing atmosphere. Here, the oxidizing atmosphere is an atmosphere containing oxygen or containing a substance capable of dissociating and oxidizing oxygen. There are an infinite number of such conditions, but considering the ease of acquisition and control, a gas atmosphere containing O 2 , CO 2 , and H 2 O is desirable. In a gas atmosphere, the oxidizing power can be easily adjusted with the concentration and pressure of the oxidizing gas, and the progress of the oxidation of coal and binder can be quickly stopped by replacing it with an inert gas after the treatment. Therefore, the processing time can be arbitrarily set. Here, the higher the concentration of the oxidizing gas and the higher the pressure, the faster the weathering proceeds. On the other hand, in the case of an oxidizing liquid atmosphere, it is difficult to quickly separate from coal and caking additive after the weathering treatment, which is not preferable for controlling the degree of weathering progress.

また、最も安価、容易かつ大量に入手可能な酸化雰囲気は大気中の空気である。従って、工業的に大量処理が求められる場合などには、酸化雰囲気として大気中の空気を用いるのが望ましい。   In addition, the cheapest, easy, and available mass atmosphere is air in the atmosphere. Therefore, when industrial mass processing is required, it is desirable to use air in the atmosphere as the oxidizing atmosphere.

風化を行う際の処理温度としては、石炭の風化現象が起こる、常温から、石炭が軟化溶融を示す直前の温度までの範囲のいずれでも実施できる。風化の進行は温度が高くなるほど速くなることから、必要な処理時間は、処理温度が高いほど短くなる。本発明者らは、処理温度が風化炭性状に及ぼす影響を調査した結果、処理温度が高いほど、風化炭の最高流動度の低下速度に対して、浸透距離の低下速度が速くなることを見出した。すなわち、高温で風化するほど、風化炭の最高流動度をなるべく下げずに、浸透距離を優先的に下げることが可能である。従って、好適な処理温度、処理時間の条件として、高温、短時間が有効である事を知見した。   The treatment temperature at the time of weathering can be any of the range from the normal temperature at which coal weathering occurs to the temperature just before coal shows softening and melting. Since the progress of weathering becomes faster as the temperature becomes higher, the necessary processing time becomes shorter as the processing temperature becomes higher. As a result of investigating the influence of the treatment temperature on the weathered coal properties, the present inventors have found that the higher the treatment temperature, the faster the decrease rate of the penetration distance with respect to the decrease rate of the maximum fluidity of the weathered coal. It was. That is, it is possible to preferentially lower the permeation distance without lowering the maximum fluidity of weathered coal as much as possible at higher temperatures. Accordingly, it has been found that high temperature and short time are effective as conditions for suitable processing temperature and processing time.

一方で、石炭を急速に風化させると、酸化発熱に伴う自然発火の恐れがあるため、散水する等の自然発火防止対策を講じる必要が生じる。また、処理温度が高すぎると、風化の速度が速いため、風化処理後の性状を制御することが困難になる。更に、石炭は、３００℃を越えたあたりから熱分解により揮発分の放出を始めるため、軟化溶融特性が変化する。また、揮発分が放出する温度域での風化処理は、可燃性のガスが酸化雰囲気の加熱条件下で存在することとなり、爆発の危険性を伴う。 On the other hand, if coal is rapidly weathered, there is a risk of spontaneous ignition due to oxidation heat generation, so it is necessary to take measures to prevent spontaneous ignition such as watering. Further, if the treatment temperature is too high, the weathering speed is high, and it becomes difficult to control the properties after the weathering treatment. Further, since coal begins to emit volatile components by thermal decomposition from around 300 ° C., the softening and melting characteristics change. In addition, the weathering treatment in the temperature range where volatile matter is released involves the danger of explosion because flammable gas exists under heating conditions in an oxidizing atmosphere.

上述した理由から、風化を行う際の処理温度としては１００℃〜３００℃、処理時間としては１〜１２０分が望ましい。最も好ましくは、風化を行う際の処理温度としては１８０℃〜２２０℃、処理時間としては１〜３０分が望ましい。   For the reasons described above, the treatment temperature during weathering is preferably 100 to 300 ° C., and the treatment time is preferably 1 to 120 minutes. Most preferably, the treatment temperature during weathering is 180 ° C. to 220 ° C., and the treatment time is 1 to 30 minutes.

なお、本発明における個別銘柄の原料炭とは、コークス製造工場に入荷する時点で単一のロットとして管理される原料炭の単位と定義する。単一のロットとして管理されるとは、そのロットからのサンプリングによる代表分析値をもって、そのロット全体の性状を表現する場合や、単一のロットとして石炭ヤードに積み付ける場合、同一の石炭槽に入れる場合、購買契約において単一のロットないしは銘柄名として取引される場合などを含む。従って、本発明における原料炭の調製とは、コークス製造工場に入荷後混合などの処理を行なう場合は含まないが、コークス製造工場に入荷する以前の段階で処理される場合にはその混合物は単一銘柄の原料炭と定義される。   The individual brand coking coal in the present invention is defined as a unit of coking coal managed as a single lot at the time of arrival at the coke manufacturing plant. When managed as a single lot, the representative analysis value obtained by sampling from that lot is used to express the properties of the entire lot, or when it is loaded into a coal yard as a single lot, Including the case where it is traded as a single lot or brand name in the purchase contract. Therefore, the preparation of coking coal in the present invention does not include the case where the processing such as mixing is performed after arrival at the coke manufacturing plant, but the mixture is simply used when it is processed at the stage prior to arrival at the coke manufacturing plant. Defined as one brand of coking coal.

本発明は、以上のように、コークス製造用原料として好適な石炭品質の範囲を、新たな軟化溶融特性の試験法によって明らかにし、そのような石炭を調製することを可能にした。本発明の方法により調製した原料を用いれば高品質のコークスが製造可能となる。   As described above, the present invention clarifies the range of coal quality suitable as a raw material for producing coke by a new test method for softening and melting characteristics, and makes it possible to prepare such coal. By using the raw material prepared by the method of the present invention, high-quality coke can be produced.

１８種類の石炭および1種類の粘結材について、浸透距離の測定を行った。使用した石炭ないし粘結材の性状を表１に示す。ここで、ＲｏはＪＩＳ Ｍ ８８１６の石炭のビトリニット平均最大反射率、ｌｏｇＭＦはギーセラープラストメータ法で測定したギーセラー最高流動度の常用対数値、揮発分（ＶＭ）、灰分（Ａｓｈ）はＪＩＳ Ｍ ８８１２の工業分析法による測定値である。   The penetration distance was measured for 18 types of coal and 1 type of caking additive. Table 1 shows the properties of the used coal or binder. Here, Ro is the maximum vitrinite average reflectance of coal according to JIS M 8816, log MF is the common logarithm of the Gieseler maximum fluidity measured by the Gieseler plastometer method, volatile content (VM), and ash content (Ash) are JIS M 8812. It is a measured value by the industrial analysis method.

図１に示した装置を用い、浸透距離の測定を行った。加熱方式は高周波誘導加熱式としたため、図１の発熱体８は誘導加熱コイルであり、容器３の素材は誘電体である黒鉛を使用した。容器の直径は１８ｍｍ、高さ３７ｍｍとし、上下面に貫通孔を有する材料として直径２ｍｍのガラスビーズを用いた。粒度２ｍｍ以下に粉砕し室温で真空乾燥した石炭試料２．０４ｇを容器３に装入し、石炭試料の上から重さ２００ｇの錘を落下距離２０ｍｍで５回落下させることにより試料１を充填した（この状態で試料層厚は１０ｍｍとなった。）。次に直径２ｍｍのガラスビーズを試料１の充填層の上に２５ｍｍの厚さとなるように配置した。ガラスビーズ充填層の上に直径１７ｍｍ、厚さ５ｍｍのシリマナイト製円盤を配置し、その上に膨張率検出棒１３として石英製の棒を置き、さらに石英棒の上部に１．３ｋｇの錘１４を置いた。これにより、シリマナイト円盤上にかかる圧力は５０ｋPaとなる。不活性ガスとして窒素ガスを使用し、加熱速度３℃／分で５５０℃まで加熱した。加熱終了後、窒素雰囲気で冷却を行い、冷却後の容器から、軟化溶融した石炭と固着していないビーズ質量を計測した。なお、上記の測定条件は、種々の条件での測定結果の比較により、発明者らが好ましい浸透距離の測定条件として決定したものであるが、浸透距離測定はこの方法に限られるものではない。   The penetration distance was measured using the apparatus shown in FIG. Since the heating method was a high frequency induction heating type, the heating element 8 in FIG. 1 was an induction heating coil, and the material of the container 3 was graphite, which is a dielectric. The diameter of the container was 18 mm, the height was 37 mm, and glass beads with a diameter of 2 mm were used as materials having through holes on the upper and lower surfaces. The sample 1 was filled by loading 2.04 g of a coal sample pulverized to a particle size of 2 mm or less and vacuum-dried at room temperature into the container 3 and dropping a weight of 200 g from the top of the coal sample 5 times at a fall distance of 20 mm. (In this state, the sample layer thickness was 10 mm). Next, glass beads having a diameter of 2 mm were placed on the packed layer of Sample 1 so as to have a thickness of 25 mm. A sillimanite disk having a diameter of 17 mm and a thickness of 5 mm is placed on the glass bead packed layer, a quartz rod is placed thereon as the expansion coefficient detecting rod 13, and a weight of 1.3 kg is placed on the quartz rod. placed. As a result, the pressure applied on the sillimanite disk is 50 kPa. Nitrogen gas was used as the inert gas, and the mixture was heated to 550 ° C. at a heating rate of 3 ° C./min. After the heating, cooling was performed in a nitrogen atmosphere, and the mass of beads not fixed to the softened and melted coal was measured from the cooled container. In addition, although said measurement conditions are what the inventors determined as measurement conditions of a preferable penetration distance by the comparison of the measurement result on various conditions, a penetration distance measurement is not restricted to this method.

なお、ガラスビーズ層の厚みは浸透距離以上の層厚となるように配置すればよい。測定時にガラスビーズ層最上部まで溶融物が浸透してしまった場合には、ガラスビーズを増量して再測定を行なう。発明者らは、ガラスビーズの層厚を変更した試験を行ない、浸透距離以上のガラスビーズ層厚があれば、同一試料の浸透距離測定値は同じになることを確認している。浸透距離の大きい粘結材の測定を行なう際には、より大きな容器を用い、ガラスビーズの充填量も増やして測定を行なった。   In addition, what is necessary is just to arrange | position so that the thickness of a glass bead layer may become layer thickness more than an osmosis | permeation distance. If the melt has penetrated to the top of the glass bead layer during measurement, the glass beads are increased and remeasured. The inventors conducted a test in which the layer thickness of the glass beads was changed, and confirmed that the permeation distance measurement values of the same sample would be the same if there was a glass bead layer thickness greater than or equal to the penetration distance. When measuring a binder with a long penetration distance, a larger container was used and the amount of glass beads filled was also increased.

浸透距離は固着したビーズ層の充填高さとした。ガラスビーズ充填層の充填高さと質量の関係をあらかじめ求め、軟化溶融した石炭が固着したビーズの質量よりガラスビーズ充填高さを導出できるようにした。その結果が（４）式であり、（４）式より浸透距離を導出した。
Ｌ＝（Ｇ−Ｍ）×Ｈ ・・・ （４）
ここで、Ｌは浸透距離［ｍｍ］、Ｇは充填したガラスビーズ質量［ｇ］、Ｍは軟化溶融物と固着していないビーズ質量［ｇ］、Ｈは本実験装置に充填されたガラスビーズの１ｇあたりの充填層高さ［ｍｍ／ｇ］を表す。 The penetration distance was the filling height of the fixed bead layer. The relationship between the filling height and the mass of the glass bead packed bed was obtained in advance, and the glass bead filling height could be derived from the mass of the beads to which the softened and melted coal was fixed. The result is equation (4), and the penetration distance was derived from equation (4).
L = (GM) × H (4)
Here, L is the penetration distance [mm], G is the mass of the filled glass beads [g], M is the mass of the beads not fixed to the softened melt [g], and H is the glass beads filled in this experimental apparatus. It represents the height of the packed bed per gram [mm / g].

浸透距離測定結果とギーセラー最高流動度（Maximum Fluidity：ＭＦ）の対数値（ｌｏｇＭＦ）の関係を図５に示す。図５より、本実施例で測定した浸透距離は最高流動度と相関は認められるが、同じＭＦであっても浸透距離の値には差がある。例えば、本装置での浸透距離の測定誤差を検討した結果、同一条件で３回試験を行った結果について標準偏差が０．６であったことを考慮すると、最高流動度がほぼ等しい石炭Ａと石炭Ｃに対して、浸透距離に有意な差が認められた。   FIG. 5 shows the relationship between the measurement results of the osmosis distance and the logarithmic value (log MF) of the Gieseler maximum fluidity (MF). From FIG. 5, the penetration distance measured in this example has a correlation with the maximum fluidity, but there is a difference in the penetration distance even with the same MF. For example, as a result of examining the measurement error of the penetration distance in this device, considering that the standard deviation was 0.6 for the result of three tests under the same conditions, coal A and For Coal C, a significant difference in penetration distance was observed.

次に、上述の（イ）〜（ニ）に該当する石炭とコークス強度との関係を調査するべく、（イ）〜（ニ）に該当しない石炭Ａを２０ｍａｓｓ％配合した配合炭、（イ）〜（ニ）に該当する石炭Ｆを２０ｍａｓｓ％配合した配合炭を作製し乾留後のコークス強度を測定した。配合組成を表２に示す。   Next, in order to investigate the relationship between the coal corresponding to the above (a) to (d) and the coke strength, the blended coal containing 20 mass% of coal A not corresponding to (b) to (d), (b) The coal blend which mix | blended 20 mass% of coal F applicable to-(d) was produced, and the coke intensity | strength after dry distillation was measured. The composition is shown in Table 2.

ここで、配合に用いた石炭の浸透距離の単純平均値は７．４ｍｍであり、Ｆ炭の浸透距離は１９．５ｍｍと、平均の２倍以上になっており（ハ）のケースに該当する。また、浸透距離が１５ｍｍ超えであるので、Ｆ炭は（ニ）にも該当する。   Here, the simple average value of the permeation distance of coal used in the blending is 7.4 mm, and the permeation distance of F coal is 19.5 mm, which is more than twice the average (C). . Further, since the permeation distance exceeds 15 mm, F charcoal also corresponds to (d).

また、式（１）、式（２）の定数ａおよびａ’を、Ａ〜Ｒ炭のうち、ｌｏｇＭＦ＜２．５の範囲にある石炭の浸透距離及び最高流動度の値をもとに回帰直線の傾きを計算し、その傾きに一致する２．８２に決定した。式（２）の定数ｂは、本発明例の測定条件での標準偏差０．６の値の５倍から、３．０に決定した。これらの式を元に、本実施例で使用した粘結材の浸透距離及び最高流動度と、上記（イ）、（ロ）の範囲との位置関係を調べた結果を図６、図７にそれぞれ示す。図６、図７より、Ｆ炭は（イ）、（ロ）の範囲の何れの条件にも該当する。これに対し、Ａ炭は（イ）〜（ニ）には該当しない。   In addition, the constants a and a ′ in the formulas (1) and (2) are regressed based on the penetration distance and the maximum fluidity value of coal in the range of log MF <2.5 among the A to R coals. The slope of the straight line was calculated and determined to be 2.82 which coincided with the slope. The constant b in the formula (2) was determined to be 3.0 from 5 times the value of the standard deviation 0.6 under the measurement conditions of the example of the present invention. Based on these equations, the results of investigating the positional relationship between the penetration distance and the maximum fluidity of the binder used in this example and the ranges of the above (A) and (B) are shown in FIGS. Each is shown. From FIG. 6 and FIG. 7, F charcoal corresponds to any condition in the range of (A) and (B). On the other hand, A coal does not correspond to (i) to (d).

従来のコークス強度を推定するための石炭配合理論において、コークス強度は主に、石炭のビトリニット平均最大反射率（Ｒｏ）と、ギーセラー最高流動度の対数値（ｌｏｇＭＦ）により決定されると考えられてきた（例えば、非特許文献２参照。）。したがって、配合炭全体の加重平均Ｒｏ、加重平均ｌｏｇＭＦは等しくなるように、種々の石炭を配合した配合炭を作製した（Ｒｏ＝０．９８、ｌｏｇＭＦ＝２．３）。ここで、石炭の粒度は粒径３ｍｍ未満１００ｍａｓｓ％となるように粉砕し、これらの石炭を使用して表２記載の２水準の配合炭（配合炭ａ、ｆ）を作製した。配合炭全体の水分は８ｍａｓｓ％になるように調整した。この配合炭１６ｋｇを、嵩密度７５０ｋｇ／ｍ3となるように乾留缶に充填し、その上に１０ｋｇの錘を乗せた状態で、炉壁温度１０５０℃の電気炉内で６時間乾留後、炉から取り出し窒素冷却し、コークスを得た。得られたコークスのコークス強度は、ＪＩＳ Ｋ ２１５１の回転強度試験法に基づき、１５ｒｐｍ、１５０回転後の粒径１５ｍｍ以上のコークスの質量割合を測定し、回転前との質量比をドラム強度ＤＩ１５０／１５として算出した。 In the conventional coal blending theory for estimating coke strength, the coke strength has been considered to be mainly determined by the coal's vitrinite average maximum reflectance (Ro) and logarithmic value (log MF) of the Gieseler maximum fluidity. (For example, refer nonpatent literature 2.). Therefore, a blended coal blended with various coals was prepared so that the weighted average Ro and the weighted average logMF of the entire blended coal were equal (Ro = 0.98, logMF = 2.3). Here, the particle size of the coal was pulverized so that the particle size was less than 3 mm and 100 mass%, and these coals were used to prepare the two-level blended coals (blended coals a and f) shown in Table 2. The water content of the entire blended coal was adjusted to 8 mass%. 16 kg of this blended charcoal was filled in a dry distillation can so that the bulk density was 750 kg / m 3, and 10 kg of weight was placed on the can, and after carbonization in an electric furnace with a furnace wall temperature of 1050 ° C., And then cooled with nitrogen to obtain coke. The coke strength of the obtained coke was measured based on the rotational strength test method of JIS K 2151 by measuring the mass ratio of coke with a particle size of 15 mm or more after 15 rpm and 150 revolutions, and the mass ratio with the pre-rotation drum strength DI150 / Calculated as 15.

配合炭ａ、ｆから製造したコークスのドラム強度の測定結果を表２に併せて示す。ＣＳＲ（ＣＯ２熱間反応後強度、ＩＳＯ１８８９４準拠）、マイクロ強度（ＭＳＩ＋６５）の測定も行なった。（イ）〜（ニ）に該当する石炭Ｆを配合した配合炭ｆの方が、（イ）〜（ニ）に該当しない石炭Ａを配合した配合炭ａに比べて強度が低いことを確認した。したがって、本発明で測定した浸透距離の値は、強度に影響を及ぼす因子であり、かつ、従来因子では説明できない因子であることが確認できた。 The measurement results of the drum strength of coke produced from blended coals a and f are also shown in Table 2. The CSR (strength after CO 2 hot reaction, conforming to ISO18894) and microstrength (MSI + 65) were also measured. It was confirmed that the blended coal f blended with the coal F corresponding to (i) to (d) was lower in strength than the blended coal a blended with the coal A not corresponding to (a) to (d). . Therefore, it was confirmed that the value of the penetration distance measured in the present invention is a factor that affects the strength and cannot be explained by a conventional factor.

以上のように浸透距離を用いた石炭評価の有効性が確認できたので、所望の浸透距離を持つ原料炭を調製する方法を検討した。ある炭鉱における５種類の炭層の浸透距離を上述と同じ方法で測定したところ、１０．３、１２．３、１５．９、２１．２、２６．８ｍｍであった。これらの等量混合物（原料炭Ｓ）の浸透距離を測定したところ、１７．９ｍｍとなり、計算上の平均値１７．３ｍｍに近い値であった。各炭層から得られた試料の混合比を変更して、加重平均浸透距離として１３．８ｍｍとなるように混合し（原料炭Ｔ）、浸透距離を測定したところ、１３．１ｍｍとなり、やはり計算値に近い値となった。原料炭ＳのｌｏｇＭＦは４．４、原料炭ＴのｌｏｇＭＦは４．３であり、原料炭Ｓは上記（イ）〜（二）に該当し、原料炭Ｔは該当しない。表２の配合炭ａにおけるＡ炭の代替として、原料炭Ｓまたは原料炭Ｔを使用し、同様の乾留試験を行った結果、原料炭Ｓを用いた場合のコークス強度（ＤＩ１５０／１５）は７７．５、原料炭Ｔを用いた場合のコークス強度が７８．７となり、原料炭Ｔを用いた場合の方がコークス強度が１．２ポイント高い結果となった（表３）。この例においても、浸透距離が小さい原料炭を用いた場合の方がコークス強度向上効果が大きい結果となった。この結果より、例えば種々の炭層から得られる石炭を混合することによって、浸透距離を所望の値に制御した原料炭を調製することが可能であり、原料炭の浸透距離を適正に調整することで、コークス強度を向上させるという効果を得ることができる。   Since the effectiveness of coal evaluation using the penetration distance was confirmed as described above, a method for preparing raw coal having a desired penetration distance was examined. It was 10.3, 12.3, 15.9, 21.2, and 26.8 mm when the penetration distance of five types of coal beds in a certain coal mine was measured by the same method as the above. When the penetration distance of these equivalent mixtures (coking coal S) was measured, it was 17.9 mm, which was close to the calculated average value of 17.3 mm. The mixing ratio of the samples obtained from each coal layer was changed and mixed so that the weighted average permeation distance was 13.8 mm (coking coal T), and the permeation distance was measured to be 13.1 mm. The value was close to. The log MF of the raw coal S is 4.4, the log MF of the raw coal T is 4.3, the raw coal S corresponds to the above (i) to (2), and the raw coal T does not correspond. As a result of conducting the same dry distillation test using coking coal S or coking coal T as an alternative to coal A in blended coal a in Table 2, coke strength (DI150 / 15) when using coking coal S is 77. .5, the coke strength when using the raw coal T was 78.7, and the coke strength when using the raw coal T was 1.2 points higher (Table 3). Also in this example, the coke strength improvement effect was larger when the raw coal having a shorter permeation distance was used. From this result, for example, by mixing coal obtained from various coal seams, it is possible to prepare raw coal with the penetration distance controlled to a desired value, and by appropriately adjusting the penetration distance of the raw coal The effect of improving the coke strength can be obtained.

さらに、上記原料炭Ｓを空気雰囲気下１５０℃で１０分間処理したところ、浸透距離が１４．０ｍｍに低下した（この原料炭を原料炭Ｕとする。）。また、上記原料炭Ｓを常温で大気中に４ヶ月間放置したところ、浸透距離が１４．１ｍｍにまで低下した（この原料炭を原料炭Ｖとする。）。この時原料炭ＵのｌｏｇＭＦ＝４．０、原料炭ＶのｌｏｇＭＦ＝４．１となり、原料炭Ｕ、Ｖとも上記（イ）〜（ニ）の範囲に該当しなくなった。原料炭Ｕ、Ｖについても表２の配合炭ａにおけるＡ炭と代替して配合し、上記の乾留試験を行なったところ、それぞれコークス強度が７８．４、７８．２となった（表４）。Ｓ炭を酸化処理せずに乾留に使用した場合の強度７７．５に比較して、酸化処理した石炭の方が強度が高い結果となり、浸透距離を適正な程度に低下させる処理によって、コークス強度を向上させることができた。なお、酸化処理を行なうと一般的にはギーセラー最高流動度（ＭＦ）も低下するので、過度に酸化させると浸透距離は所定値よりも下がるものの、ＭＦ値も低下してしまい、コークス強度が低下する可能性がある点には注意が必要である。このようなＭＦ低下は、他の高ＭＦ炭の配合率を増加するなどの処理により補うことができるが、コストアップになる場合もある。酸化処理による浸透距離の調整にはこのような問題があるため、適度な酸化処理に留めることが望ましい。ただし、異なる炭層の石炭を混合して浸透距離を調整する場合には、ＭＦ低下の問題は発生しないため、混合する原料石炭の品位に応じて浸透距離の調整を行なうことができる。   Furthermore, when the raw coal S was treated at 150 ° C. for 10 minutes in an air atmosphere, the permeation distance was reduced to 14.0 mm (this raw coal is referred to as raw coal U). Further, when the raw coal S was left in the atmosphere at room temperature for 4 months, the permeation distance decreased to 14.1 mm (this raw coal is referred to as raw coal V). At this time, log MF of the raw coal U = 4.0 and log MF of the raw coal V = 4.1, and the raw coals U and V no longer fall within the above ranges (A) to (D). Coking coals U and V were blended in place of coal A in blended coal a in Table 2 and subjected to the above dry distillation test, resulting in coke strengths of 78.4 and 78.2, respectively (Table 4). . Compared to the strength of 77.5 when S coal is used for dry distillation without oxidation treatment, the strength of the oxidized coal is higher, and the coke strength is reduced by the treatment that reduces the permeation distance to an appropriate level. Was able to improve. In general, the Gieseler maximum fluidity (MF) is also reduced when oxidation is performed. However, if excessive oxidation is performed, the permeation distance is lower than a predetermined value, but the MF value is also reduced, and the coke strength is lowered. It is important to note that this may happen. Such a decrease in MF can be compensated for by a process such as increasing the blending ratio of other high MF charcoal, but may increase the cost. Since there is such a problem in the adjustment of the permeation distance by the oxidation treatment, it is desirable to keep the oxidation treatment moderate. However, when the penetration distance is adjusted by mixing coals of different coal beds, the problem of MF reduction does not occur, so the penetration distance can be adjusted according to the quality of the raw coal to be mixed.

なお、図５によれば、ｌｏｇＭＦと浸透距離の相関のバラツキが大きくなるのが、ｌｏｇＭＦ＞２以上の領域であることがわかる。上述のＲｏとＭＦを用いた配合理論においては、配合炭の加重平均ｌｏｇＭＦを制御するため、ＭＦと浸透距離の相関が良い場合には、ｌｏｇＭＦを制御すれば浸透距離もおよそ決まってくる。しかし、ｌｏｇＭＦ＞２すなわち、ＭＦ＞１００ｄｄｐｍの領域では、両者の相関が悪いため、ｌｏｇＭＦを所定の値に制御しても浸透距離が異なることによってコークス強度が変わる場合がある。したがって、本発明による原料炭の調製方法がより有効に機能するのは、ＭＦ＞１００ｄｄｐｍの原料炭を用いた場合であることがわかる。   According to FIG. 5, it can be seen that the variation in the correlation between the log MF and the permeation distance increases in a region where log MF> 2 or more. In the above blending theory using Ro and MF, the weighted average log MF of the blended coal is controlled. Therefore, when the correlation between MF and penetration distance is good, the penetration distance is roughly determined by controlling log MF. However, in the region of log MF> 2, that is, MF> 100 ddpm, the correlation between the two is bad, and even if the log MF is controlled to a predetermined value, the coke strength may change depending on the penetration distance. Therefore, it can be seen that the method for preparing raw coal according to the present invention functions more effectively when raw coal with MF> 100 ddpm is used.

１ 試料
２ 上下面に貫通孔を有する材料
３ 容器
５ スリーブ
７ 温度計
８ 発熱体
９ 温度検出器
１０ 温度調節器
１１ ガス導入口
１２ ガス排出口
１３ 膨張率検出棒
１４ 錘
１５ 変位計
１６ 円形貫通孔
１７ 充填粒子
１８ 充填円柱 DESCRIPTION OF SYMBOLS 1 Sample 2 Material which has a through-hole in the upper and lower surfaces 3 Container 5 Sleeve 7 Thermometer 8 Heating element 9 Temperature detector 10 Temperature controller 11 Gas inlet 12 Gas outlet 13 Expansion rate detection rod 14 Weight 15 Displacement meter 16 Circular penetration Hole 17 Packing particle 18 Packing cylinder

Claims (13)

コークス製造原料として単独で、または他の石炭と配合して用いる個別銘柄の石炭を調製する際に、前記銘柄の石炭の浸透距離を所定の値以下に調整することを特徴とするコークス製造用石炭の調製方法。   Coal for producing coke characterized by adjusting the permeation distance of said brand of coal to a predetermined value or less when preparing individual brand of coal used alone or in combination with other coal as a raw material for coke production Preparation method. 複数の石炭を混合してコークス製造用石炭を製造する際に、少なくとも一つの石炭について、該石炭の浸透距離を所定の値以下に調整してから混合することを特徴とするコークス製造用石炭の調製方法。   When producing coal for coke production by mixing a plurality of coals, at least one coal is mixed after adjusting the permeation distance of the coal to a predetermined value or less. Preparation method. 前記石炭銘柄のギーセラー最高流動度を１００ｄｄｐｍ以上に調整することを特徴とする請求項１または請求項２に記載のコークス製造用石炭の調製方法。   The method for preparing coal for coke production according to claim 1 or 2, wherein the coal brand has a Gieseler maximum fluidity of 100 ddpm or more. 前記調製する石炭銘柄の浸透距離の所定の値を下記式（１）にて規定することを特徴とする請求項１ないし請求項３のいずれか１項に記載のコークス製造用石炭の調製方法。
浸透距離＝１．３×ａ×ｌｏｇＭＦｃ （１）
但し、ａは、ギーセラー最高流動度ＭＦの常用対数値ｌｏｇＭＦ＜２．５の範囲にある石炭の少なくとも１種以上の浸透距離及びｌｏｇＭＦを測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数であり、
ＭＦｃは、調製する石炭のギーセラー最高流動度（ｄｄｐｍ）である。 The method for preparing coke-producing coal according to any one of claims 1 to 3, wherein a predetermined value of a permeation distance of the coal brand to be prepared is defined by the following formula (1).
Permeation distance = 1.3 × a × logMFc (1)
However, a measures the penetration distance and log MF of at least one kind of coal in the range of the common logarithm log MF <2.5 of the Gieseler maximum fluidity MF, and uses the measured value to calculate a regression line passing through the origin. A constant in the range of 0.7 to 1.0 times the coefficient of logMF at the time of creation,
MFc is the Gieseler maximum fluidity (ddpm) of the coal to be prepared. 前記ａが、１．７５＜ｌｏｇＭＦ＜２．５０の範囲にある石炭の少なくとも１種以上の浸透距離及びギーセラー最高流動度ＭＦの常用対数値ｌｏｇＭＦを測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数であることを特徴とする請求項４に記載のコークス製造用石炭の調製方法。   The at least one penetration distance of coal in the range of 1.75 <log MF <2.50 and the common logarithm log MF of the Gieseler maximum fluidity MF are measured, and the measured value is used to pass through the origin. 5. The method for preparing coal for coke production according to claim 4, wherein the constant is in the range of 0.7 to 1.0 times the log MF coefficient when the regression line is created. 前記調製する石炭銘柄の浸透距離の所定の値を下記式（２）にて規定することを特徴とする請求項１ないし請求項３のいずれか１項に記載のコークス製造用石炭の調製方法。
浸透距離＝ａ’×ｌｏｇＭＦｃ＋ｂ （２）
但し、ａ’は、ギーセラー最高流動度ＭＦの常用対数値ｌｏｇＭＦ＜２．５の範囲にある石炭の少なくとも１種以上の浸透距離及びｌｏｇＭＦを測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数であり、
ｂは、前記回帰直線の作成に用いた銘柄から選ばれる１種類以上の同一試料を複数回測定した際の標準偏差の平均値以上で、前記平均値の５倍以下とする、定数であり、
ＭＦｃは、調製する石炭のギーセラー最高流動度（ｄｄｐｍ）である。 The method for preparing coke-producing coal according to any one of claims 1 to 3, wherein a predetermined value of a permeation distance of the coal brand to be prepared is defined by the following formula (2).
Permeation distance = a ′ × logMFc + b (2)
However, a ′ is a regression line passing through the origin by measuring at least one permeation distance and log MF of coal in the range of logarithm log MF <2.5 of logarithm of the highest flow rate MF of Gieseer. Is a constant in the range of 0.7 to 1.0 times the coefficient of log MF when
b is a constant that is not less than the average value of the standard deviation when measuring one or more types of the same sample selected from the brands used to create the regression line, and not more than 5 times the average value,
MFc is the Gieseler maximum fluidity (ddpm) of the coal to be prepared. 前記ａ’は、１．７５＜ｌｏｇＭＦ＜２．５０の範囲にある石炭の少なくとも１種以上の浸透距離及びギーセラー最高流動度ＭＦの常用対数値ｌｏｇＭＦを測定し、その測定値を用いて原点を通る回帰直線を作成した際のｌｏｇＭＦの係数の０．７から１．０倍の範囲の定数であることを特徴とする請求項６に記載のコークス製造用石炭の調製方法。   The above a ′ measures the common logarithm log MF of at least one kind of penetration distance of coal in the range of 1.75 <log MF <2.50 and Gieseler maximum fluidity MF, and uses the measured value to determine the origin. The method for preparing coal for coke production according to claim 6, wherein the constant is in the range of 0.7 to 1.0 times the coefficient of log MF when a regression line passing through is created. 浸透距離の所定の値として、粒径２ｍｍ以下に調製した石炭を０．８ｇ／ｃｍ3の充填密度で容器内に厚さ１０ｍｍに充填して試料とし、該試料の上に直径２ｍｍのガラスビーズを配置し、該ガラスビーズの上部に５０ｋＰａの荷重を負荷しつつ、３℃／分の加熱速度で５５０℃まで前記試料を加熱する際に、前記ガラスビーズへ浸透した溶融試料の浸透距離の測定値で１５ｍｍとすることを特徴とする請求項１ないし請求項３のいずれか１項に記載のコークス製造用石炭の調製方法。 As a predetermined value for the permeation distance, coal prepared to a particle size of 2 mm or less is packed into a container with a packing density of 0.8 g / cm 3 to a thickness of 10 mm, and a glass bead with a diameter of 2 mm is placed on the sample. When the sample is heated to 550 ° C. at a heating rate of 3 ° C./min while a load of 50 kPa is applied to the top of the glass beads, the measurement of the penetration distance of the molten sample that has penetrated into the glass beads The method for preparing coal for coke production according to any one of claims 1 to 3, wherein the value is 15 mm. 配合炭を構成する複数種類の石炭の種類を予め決定し、それらの石炭の浸透距離の平均値に対して２倍以上の値を前記浸透距離の所定の値とすることを特徴とする、請求項１ないし請求項３のいずれか１項に記載のコークス製造用石炭の調製方法。   A plurality of types of coal constituting the blended coal are determined in advance, and a value that is twice or more the average value of the penetration distance of the coal is set as the predetermined value of the penetration distance. The method for preparing coal for producing coke according to any one of claims 1 to 3. 個別銘柄の石炭を調製する際に、産出場所の異なる複数種類の石炭を混合して、浸透距離を調整することを特徴とする請求項１ないし請求項９のいずれか１項に記載のコークス製造用石炭の調製方法。   The coke production according to any one of claims 1 to 9, wherein when preparing individual brand coal, a plurality of types of coal from different production locations are mixed to adjust the permeation distance. Coal preparation method. 石炭を、常温以上の温度で、Ｏ２、ＣＯ２、Ｈ２Ｏの１種以上の成分を含む雰囲気下に置く処理を行なうことで該石炭の浸透距離を低下させて調整することを特徴とする請求項１ないし請求項９のいずれか１項に記載のコークス製造用石炭の調製方法。 It is characterized by adjusting the permeation distance of the coal by performing a process of placing the coal in an atmosphere containing one or more components of O 2 , CO 2 , and H 2 O at a temperature of normal temperature or higher. The method for preparing coal for producing coke according to any one of claims 1 to 9. 前記処理が、処理温度１００℃〜３００℃、処理時間１〜１２０分で行われる請求項１１に記載のコークス製造用石炭の調製方法。   The method for preparing coal for coke production according to claim 11, wherein the treatment is performed at a treatment temperature of 100C to 300C and a treatment time of 1 to 120 minutes. 前記処理が、処理温度１８０℃〜２００℃、処理時間１〜３０分で行われる請求項１２に記載のコークス製造用石炭の調製方法。   The method for preparing coal for coke production according to claim 12, wherein the treatment is performed at a treatment temperature of 180C to 200C and a treatment time of 1 to 30 minutes.
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